Jermain entered the fray at the start of the second half with England trailing 2-0 against Croatia in a game they only had to draw to progress to next summer's finals.
It took the striker a little over 10 minutes to help hand England a lifeline when he was pulled back by Simunic in the box and Frank Lampard netted the penalty for 2-1. It was soon 2-2 via Peter Crouch only for Mladen Petric to fire home what turned out to be the winner with 11 minutes left.
Darren was thrown on just after that goal and had England's final chance when he did well to hold off Simic and could only look in agony as his effort grazed the roof of the net.
England ended up third in the group as Croatia and Russia progress.
Teemu Tainio's dream of playing in the finals of a major tournament with Finland is on hold again after the Finns drew 0-0 in Portugal. Teemu played 69 minutes in Porto in a game Finland had to win to progress, the draw was good enough for Portugal and Finland will finish third or fourth.
Dimitar Berbatov was on target again for Bulgaria as they completed their qualifying campaign with a 2-0 win in Slovenia. They will also finish third in their group.
Elsewhere, Didier Zokora's Ivory Coast beat Qatar 5-2 in a friendly.
Tom Huddlestone helped England Under-21s take a step nearer the European U21 Championship play-offs in Portugal on Tuesday night.
The midfielder played a full 90-minute shift as Stuart Pearce's men came from 1-0 down to draw 1-1 in Agueda thanks to Adam Johnson's equaliser.
Tom's set-pieces caused problems for the Portuguese all night and he tried his luck three times in the second half, the third attempt, a volley from James Milner's cross, his closest.
Victory over the Republic of Ireland in their next group fixture in February should all-but book their place in the play-offs for the finals in Sweden in 2009.
It won't be as easy going for Younes Kaboul and France's Under-21s after they were beaten 4-2 by Wales at Cardiff. Younes captained the side, played the full 90 minutes at Ninian Park and went close with a header in the second half but the result brings Wales right back into the picture in terms of making the play-offs.
Danny Rose played his part as England Under-18s toppled Ghana 2-0 in a friendly at Gillingham.
The young forward won a penalty for his side in the first half - the spot kick was missed - created a chance for goalscorer Daniel Welbeck and was then denied by Ghana keeper Joseph Addo. He was replaced after 80 minutes.
Paul Stalteri had a game to forget as Canada faced South Africa for the first time in a friendly at the ABSA Stadium in Durban.
The most senior player in the side earning his 62nd cap, full-back Paul conceded a penalty to allow the hosts to take a 2-0 lead at the end of the first half and was then sent off for a second yellow card after 79 minutes. It ended 2-0 to South Africa.
Jermain Defoe and Darren Bent did their best to change the course of a disastrous night as England crashed out of contention for Euro 2008.