Sven-Goran Eriksson has been overlooked for the Ukraine national team job, with the FFU instead opting for Mikhail Fomenko to take over from Oleg Blokhin.
Fomenko, a former Dynamo Kiev manager, was selected as the top candidate, despite confirmation that Eriksson had been approached over the role earlier this month.
Ukraine had been looking for a new coach since Blokhin resigned to take charge of Dynamo in September, and Fomenko says he will repay the faith shown in him by his compatriots.
"I want to thank the board and president of the FFU for their trust," he told the FFU's official website.
"I understand the responsibility entrusted in me and challenges that face the national team of Ukraine.
"Our primary objective is to get to the finals of the World Cup in Brazil, and for this we need to take at least second place in our qualifying group."
Harry Redknapp was also linked with the position before taking the reins at Premier League side QPR, while former Ukraine captain Andriy Shevchenko declined the role.