Scotland's fantastic start to Euro 2008 qualifying came to a halt as they toppled to defeat in Kiev.
Scotland were under pressure for long spells
The Scots adopted a defensive approach but their stubborn resistance was broken on the hour by a close range shot from Olexander Kucher.
Kenny Miller hit the crossbar with a speculative effort and headed a wonderful chance wide on 80 minutes.
But Scotland lost Steven Pressley to a red card and Ukraine captain Andriy Shevchenko converted a late penalty.
The sending off and the penalty were harsh but Scotland can have no complaints about the result.
Ukraine enjoyed the lion's share of possession, with Scotland sitting in deep and inviting the home team to come at them.
On a rare Scotland burst forward, Paul Hartley released Darren Fletcher down the right flank but, with Miller speeding in on goal, the midfielder's weak cut-back was easily intercepted.
The Scots were given their first real scare following a scramble from a 26th minute corner but Shevchenko could only poke the ball into Craig Gordon's arms from close range.
Andriy Voronin gave the massed ranks of Scots defenders the slip five minutes before the interval but goalkeeper Gordon was able to beat away the forward's powerful strike.
Two minutes after the break, Scotland enjoyed a huge slice of fortune when Shevchenko hit the woodwork.
David Weir was at full stretch to block the striker's first effort and, when the ball broke back to the captain, his shot rolled beyond Gordon but struck the post.
The yellow shirts of Ukraine continued to swarm forward and a blistering shot from Andriy Nesmachny was expertly headed to safety by Gary Caldwell.
But the home side took advantage of a lucky break to take the lead.
James McFadden appeared to have cleared a Shevchenko free-kick but the ball hit Vyacheslav Sviderski and the ball ran through to Kucher, who drilled a shot home through Caldwell's legs.
Kenny Miller was deployed as Scotland's lone striker
Gordon had his hands warmed by a swerving strike from Shevchenko before Scotland went close to an unlikely equaliser.
Miller's dipping delivery from the right deceived goalkeeper Olexander Shovkovsky and bounced off the crossbar.
The Celtic striker then passed up a glorious chance with ten minutes remaining.
Robbie Neilson, making his Scotland debut, swung in a great cross and the unmarked Miller dipped in to head but skewed his effort wide from eight yards out.
Pressley was ordered off for bringing Shevchenko down as the striker ran in on goal four minutes from time.
And shortly after the Chelsea star collapsed in the box while tussling with Neilson to win and send home a 90th minute spot-kick.
Pressley will now miss the next match at home to Georgia in March, along with McFadden and Fletcher who both picked up their second bookings of the campaign.
Ukraine: Shovkovskiy, Nesmachniy, Sviderskiy, Kucher, Rusol, Tymoschuk, Shelayev, Gusev (Milevskiy 62), Kalinichenko (Vorobey 76), Shevchenko, Voronin (Shershun 90).
Subs Not Used: Shust, Rykun, Nazarenko, Gay.
Goals: Kucher 60, Shevchenko 90 pen.
Scotland: Gordon, Neilson (McManus 89), Weir, Pressley, Graham Alexander, Caldwell, Ferguson, Fletcher, Hartley, Miller, McFadden (Boyd 73).
Subs Not Used: Neil Alexander, McCulloch, Teale, Severin, Brown.
Sent Off: Pressley (86).
Booked: McFadden, Fletcher, Neilson.
Ref: Martin Hansson (Sweden).