Matthews went head-to-head with European champion Sonny Colbrelli (Bahrain Victorious) in the final dash to the line and ended up winning with a clear margin.
Colbrelli collapsed a few minutes after the race with an apparent heart attack. The Italian champion reportedly regained consciousness before being transferred to hospital.
Matthews, unaware of Colbrelli's issues, was very happy to have broken a winless streak which had dogged his return season at Australian WorldTour squad BikeExchange-Jayco.
"It’s been a long time… sorry, you can see how much this means to the team," said Matthews as his post-race interview was interrupted for a hug from Chris Juul-Jensen. "It’s been a long time without a victory for me now. To come back to a finish that I know from a few years ago to now win again, it means so much.
"My wife and dog were here to support me today, it means so much to be able to go and give my wife a massive hug."
Matthews was victorious on the same finish in 2019, he also went on to claim another win later in the race that same year, with the perennial classics contender looking in good form at present.
"This course suits me quite well," said Matthews, "a hard race, then an uphill sprint to the finish. I think knowing the finish from a couple of years ago helped me.
"The team did a great job today, splitting the race in the crosswind, it was maybe a little too far to go, we decided to back it off and save it for the final."
The early break was to have their regular rhythm of get out to a big lead and then play cat and mouse with the peloton abruptly halted as the race exploded midway through.
With 90 kilometres left in the race, the peloton hit a flat, exposed section, with BikeExchange-Jayco and Israel-Premier Tech forcing splits at the front of the main group with a determined push. There were further splits behind among the chasers, but they eventually came back together to form a united pursuit of the escapees.
Simon Yates of BikeExchange-Jayco was the main contender in the 18-man move that bridged across to the initial break, forming a dangerous group of 24 in front. The gap stretched out to 55 seconds, but the organised chase behind and the distance remaining discouraged the front split from pushing on and the race came back together with just under 50 kilometres to go.
Jonathan Caciedo (EF-Nippo) attacked immediately after the catch, Nans Peters (Groupama-FDJ) bridged to join but unfortunately punctured just as he reached the Ecuadorian, dropping back leaving the EF-Nippo rider as the lone leader.
Pieter Serry (QuickStep-AlphaVinyl), Bruno Armirail (Groupama-FDJ), Theo Delacroix (Intermarche Wanty Gobert Materiaux), Jonas Hvideberg (Team DSM), Alex Molenaar (Burgos-BH) joined Caicedo at the head of affairs and pushed out to a maximum lead of a minute and 15 seconds before the main group gathered to form a determined chase.
Australian Jai Hindley (BORA-hansgrohe) suffered a mechanical that saw the Giro d’Italia 2020 runner-up have to stop twice before regaining contact with the peloton, where he would eventually finish safely in the bunch. Another overall contender who suffered ill-fortune was Richard Carapaz (INEOS Grenadiers) with the Olympic road race champion crashing within the final 30 kilometres, but looking to suffer little in the way of negative effects as he made his way swiftly back into the main bunch.
At the pointy end of the race, Rohan Dennis (Jumbo-Visma) was a consistent presence at the front of the main split and then the reformed peloton, and it was the Australian national time trial champion who brought the breakaway back to heel with seven kilometres remaining in the race and a reduced bunch sprint in the offing.
Matthews kept himself in good position throughout the final kilometres, just off the lead riders as QuickStep Alpha Vinyl took up the pace on a small hill and then through the technical corners heading into town. As the sprinters prepared for the finish, late attackers tried to pre-empt the bunch dash on the uphill run to the line with Sylvan Moniquet (Lotto Soudal) and Richard Carapaz (INEOS Grenadiers) attempting to shoot clear.
They were marked and it came down to a drag race to the line between Colbrelli and Matthews, one taking each side of the road as the Australian showed superior power to claim the win after the hard stage.
Colbrelli suffered what was said to be a heart attack shortly after the stage, he was given medical attention at the scene and regained consciousness before being transferred to hospital in an ambulance.
Colbrelli had been in good form, but had been struck down with bronchitis during a recent outbreak at Paris-Nice, the sprinter having to pull out of Milan-Sanremo as well. Bahrain Victorious issued a short statement after the race.
The Volta a Catalunya continues with Stage 2 from L'Escala to Perpinyàl, a 202.5-kilometre route that is expected to finish in a bunch sprint with the majority of climbing in the middle portion of the parcours. Watch the race on SBS VICELAND and SBS On Demand from 0115 AEDT.
