Spain had to wait a little bit longer than anticipated for their first gold of the championships when Russian Yuliya Zarudneva spoilt the script by beating world champion and home favourite Marta Dominguez in the steeplechase final.
Zarudneva went to the front from the gun with Dominguez, wearing her trademark pink headband with matching running shoes, shadowing her.
The noise from the half-full stadium was deafening, as the crowd urged Dominguez to victory but the world silver medallist gained revenge for her defeat in Berlin last year, pulling clear off the final water jump to win in 9:17.57.
The Spanish flag-waving and cheering was finally rewarded in the last race of the evening when an astonished Arturo Casado finished strongly to take the 1500M title in 3:42.74.
Lemaitre appeared to be staring defeat in the face after a poor start in the 200 left him out of the medal places and some five metres behind Britain's Christian Malcolm going into the straight.
But the 100 metres champion produced an astonishing late burst of speed and, with a roar, lunged past a surprised Malcolm to snatch victory by 0.01 seconds in 20.37 and become the first Frenchman to do the European sprint double.
Russia's women enjoyed a golden fiesta with five victories, including a sweep of the 400 medals.
Tatyana Firova led her compatriots home in the one-lap sprint, edging out Kseniya Ustalova to win in 49.89. European indoor champion Antonina Krivoshapka completed the trio.
Russian pole vaulter Svetlana Feofanova secured her second European title, eight years after her first with a clearance of 4.75 metres. Germany's Silke Spiegelburg took silver with 4.65 on countback from compatriot Lisa Ryzih.
There was a championship record on 52.92 for Natalya Antyukh in the 400 hurdles.
The 'wrong' Borlee brother won the men's 400 title when Kevin upset the form book to beat his twin and race favourite Jonathan to gold, timing 45.08.