Yevhenia Tymoshenko, 25, married Briton Sean Carr, 36, at an Orthodox chapel in the Ukrainian capital Kiev.
Mr Carr led his bride out to waiting press and well-wishers to the sound of bells and Scottish bagpipes.
Well-wishers - many of them elderly Ukrainian women - shouted "happiness" in Ukrainian and English.
The couple posed briefly in front of the press and sipped champagne - after toasts Mr Carr threw his champagne glass onto the ground to the delight of his mother-in-law, BBC reported.
Many of the well-wishers came to see Yulia Tymoshenko, who wore her usually braided hair loose over her shoulders.
"The sort of woman like Yulia Volodymyrovna comes around only once in 100 years," said Lyudmila Zaleskaya, 61, in reference to the former prime minister.
"Our government, our whole country should be proud of a woman like her. I'm here because of Yulia."
The Timoshenkos are a wealthy and powerful family. Yulia Timoshenko is known as the Goddess of the (Orange) Revolution because of the role she played in helping Viktor Yushchenko to overturn the results of a rigged election and win power in December last year.
Yevgenia has lived in the UK since the age of 14 and is in the process of completing her studies at the London School of Economics. The couple met at an Egyptian tourist resort.
Mr Carr is a former shoe salesman who sings with the heavy metal band Death Valley Screamers. He also has a young daughter by a former partner who has given an interview to a British tabloid newspaper in which she said that Mr Carr regularly beat her up and in 2002 broke her teeth, upper jaw and collarbone.
Mr Carr was found guilty of assault and was sentenced to two years' probation and ordered to take relationship and anger management counselling, Independent reported.
Mr Carr has moved his Harley-Davidson bike and giant rottweiler to his new home outside Kiev, which he shares both with his new wife and mother-in-law - who he apparently now calls 'mama'. While many Ukrainians seem bewildered by Miss Tymoshenko's unusual choice, she stresses their feelings are mutual and just how much she loves his music.
Yulia Tymoshenko has said: "He is a nice person and he adores my daughter, that's the most important thing."
The wedding ceremony went smoothly yesterday. There was bagpipe music and Ukrainian folk songs and Mr Carr and the Death Valley Screamers were due to perform at the reception afterwards.
Many of the some 150 guests sported colourful tattoos and piercings. The couple briefly posed for photographs but had decided they would not take questions from journalists.
The Ukraine wedding is expected to be followed by a trip to Mr Carr's native Yorkshire.
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