A talented and hugely skilful Portuguese team secured a thoroughly deserved 3-1 victory - yet still failed to qualify for the semi-finals as Italy and Switzerland played out a goalless draw in Basle that sent both sides through - while Defoe, despite his proven ability to nick a goal out of nothing, was strangely substituted as England trailed 2-1 midway through the second half.
Defoe was one of three changes to the team that had started Monday's 2-1 defeat against Italy in Basle. He came in for Peter Crouch, while defender Chris Riggott and the suspended Sean Davis made way for Jermaine Pennant and Jonathan Greening, as Platt reverted back to the more trusted 4-4-2 formation and added some much-needed pace to the side.
Portugal, meanwhile, had seven new faces in their starting line-up following their surprise 2-0 defeat to hosts Switzerland on Monday, and also fielded 19-year-old Hugo Viana, high in confidence after his earlier call-up to Portugal's World Cup finals squad.
The Portuguese started by far the livelier team and, after missing two good chances early on, it was no real surprise when they took the lead after just eight minutes. Semedo collected the ball on the right before whipping in a low cross that was touched back by Neca for Teixeira to slam past Paul Robinson from 10 yards out.
12 minutes later, the lead was doubled, as the dangerous Semedo again skipped down the right and turned inside Konchesky, whose ill-timed lunge was punished by referee Ersoy, who pointed straight to the penalty spot. Makukula stepped up and stroked the ball home from 12 yards.
Frustration then boiled over to anger for England, as Luke Young and David Dunn were both booked for fouls on Ribeiro, while Platt attempted to kickstart his team by replacing Greening with Newcastle United's rangy striker Shola Ameobi.
The change added further impetus to the England attack and played a direct part in the valuable goal that provided hope just three minutes before the break. Ameobi received a short pass from Prutton and dribbled into the box before squaring the ball to Alan Smith, who controlled well and tucked home left-footed from eight yards out.
Defoe also looked sharp in the closing moments of the half without enjoying any real chances, although he almost created an equaliser with a surging run into the box and low cross that was handled well by goalkeeper Leite.
Buoyed by their resurgence, England made a much brighter start to the second period and Luke Young went close with a cross-shot from the right, while Smith missed a good chance to double his tally when he screwed a shot wide after being sent clear by Prutton.
Portugal were in no mood to give up their lead without a fight, though, and missed a glorious chance to restore their two goal advantage after 51 minutes, when Semedo cut the ball back for Neca, whose mis-kick fell perfectly for Makukula six yards out, but Robinson came to the rescue - as he has done on several occasions throughout this tournament - with a fantastic block to keep the ball out.
Defoe was then replaced by Zamora with 24 minutes remaining - and three minutes later England's participation in the competition was all but finished, as substitute Miguel skipped through the middle and fed the World Cup-bound Viana, who turned Konchesky before firing low past Robinson.
Zamora and Dunn both wasted decent chances in the closing stages, and England's youngsters were left to dwell on what might have been.
Defoe did nothing in this tournament to suggest that his future in international football won't be extremely bright, and he will now look forward to a well-earned rest before returning to pre-season training with the Hammers for a hopefully prolific Premiership campaign at Upton Park.
England (4-4-2): Robinson; Young, Knight, Barry, Konchesky; Pennant (Parker 77), Prutton, Dunn, Greening (Ameobi 31); Smith, Defoe (Zamora 66).