Spain, the most consistent qualifiers in European football for a decade, crashed to a shock 1-0 home defeat to Greece in the last of Saturday's 19 European Championship qualifying matches.
Stelios Giannakopoulos gave Greece their Group Six success with a stunning shot to inflict a first competitive home defeat on the Spaniards in 12 years.
A seven-goal thriller between Ukraine and Armenia and a Dutch scoring record for Patrick Kluivert were among the other highlights. But the big shock of the night took place in Zaragoza.
Spain had dominated for most of the first half before Giannakopoulos lashed in his spectacular effort two minutes before the half-time interval.
Greece had defender Stelios Venetidis sent off in the 82nd minute but held out to hand Spain their first meaningful home defeat since they went down 2-1 to France in a European championship qualifier in 1991.
The result made Serhiy Fyodorov's injury-time winner for Ukraine even more valuable than it had seemed hours earlier when it secured a 4-3 home win over Armenia.
Spain continue to lead the group on 10 points, but are now just one ahead of both Ukraine and Greece, who meet in Athens on Wednesday.
A contender for goal of the day came in Tallinn where Estonian defender Teet Allas met a goalkick 40 metres out and shot it back into the net to send Estonia on their way to a 2-0 win over Andorra.
Estonia climbed to second in Group Eight on eight points, three points behind leaders Bulgaria who were held 2-2 in Sofia by Belgium, who have seven points, the same as Croatia.
Austria went down to a 1-0 defeat in Moldova - who had lost all four or their previous Group Three qualifiers. Debutant Viorel Frunze got the goal after an hour.
The Austrians now look out of it on six points, four behind the non-playing Czech Republic and seven behind Holland.
The Dutch beat Belarus 2-0 away, helped by a goal from Kluivert, who duly became his country's all-time leading scorer on 38, overtaking Dennis Bergkamp.
Holland opened the scoring with a superb strike from Marc Overmars, who shot from 20 metres into the top corner two minutes after coming on.
Group Four continues to provide twists and turns as leaders Latvia fell to their first defeat. Hungary came from behind to win 3-1 in Budapest.
Latvia cling on to top spot on 10 points but Hungary and Sweden, who thrashed San Marino 6-0 away and have a game in hand, both have eight, with Poland on seven.
It is just as close in Group Two, where Denmark's 1-0 home win over Norway, courtesy of an early Jesper Gronkjaer goal, and Romania's 2-0 home success against Bosnia & Montenegro have closed things up.
Denmark and Norway have 10 points, Romania, beaten 5-2 at home by the Danes in March, nine and Bosnia six.
Turkey returned to the top of Group Seven with a 1-0 away win over Slovakia. They have 12 points, two more than England who host Slovakia on Wednesday.
France edged closer to qualification despite not playing as their closest rivals Slovenia and Israel drew 0-0 in Group One.
The defending champions have 15 points, Slovenia 10 and Israel eight. Cyprus won 2-1 in Malta to move on to seven.