Devlin, who headed all his goals following curling corner kicks into the penalty area by Yazalde Santos, opened the scoring midway through the first half after Scottish had missed a handful of excellent opportunities at the IJ Bathe Field.
They were made to pay, too, as Portuguese hit back to lead 2-1 shortly after the break.
Scottish then survived as Portuguese squandered three clear chances to extend their lead.
Shortly after having defender Carlos Figueira sent off after collecting two yellow cards from Polish referee Machic Murmot, who issued ten yellow cards in total, Devlin netted his second six minutes from the end to force extra-time.
A clumsy challenge on Devlin, Jersey’s Footballer of the Year, led to Ross Crick firing the Scots ahead from the penalty spot before Devlin notched his third to make it 4-2.
Paul Duxbury then broke through the heart of Portuguese’s defence to complete the win with a fine finish low into the corner of the net.
Carlos Ferreira scored both Portuguese goals, two fine strikes from outside the penalty, his first after Artur Calaca’s free kick deflected off a defensive wall before looping up and coming back into play off a crossbar.
Ferreira’s second was a fine finish, his left-foot shot arrowing into a top corner to give Portuguese a 2-1 advantage.
Scottish picked up three injuries last night as James Scott and Craig Ferey injured wrists after landing heavily on the hard surface and Chris McNabb turned his ankle.
The trio are all likely to be sidelined for Scottish’s second-round match against Jersey Wanderers on Thursday.
Also last night, Grouville defeated First Tower 2-1 at Le Boulivot.
Jamie Drummond and Luc Le Mière were on target for the hosts before Mark Lucas reduced the deficit with a fine volley which struck the underside of a crossbar on its way in.
Grouville now host St Paul’s on Thursday.
Division I Magpies were beaten 6-4 after extra-time by Division II Jersey Wanderers at the Hockey Club.
David Ibbotson and junior Pierce Cummins scored twice each for Wanderers, with Paul Banahan and junior David Kenyon adding singles.
Magpies scored through Aaron Gouveia (two), Manny Fernandes and Steve Cumming.
Trinity play Sporting Academics at Les Quennevais tomorrow while Thursday’s third game is St Peter and Rozel Rovers at St Peter.
All matches kick off at 6 pm.
