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Ukrainian-Russian relations have been strained, but seemed to be improving two weeks ago, as Moscow's ambassador to Kiev arrived after a long absence.
The row comes days before the second and decisive round of Ukraine's presidential election, in which relations with Russia are an issue.
Sensitive time
Ukraine said that the five alleged Russian spies were caught possessing a camera concealed inside a pen, other espionage equipment and $2,000 (£1,250) - a reported bribe for a Ukrainian contact.
The head of Ukraine's security service says that the five were trying to obtain military secrets.
The FSB said its actions were a response to the recruitment of Russians by the Ukrainian security services.
The accusations come at a highly sensitive time.
The mutual recriminations also come just two weeks after Russia sent an ambassador to Ukraine, ending a five-month diplomatic rift.
And on Sunday, Ukrainians will vote in an election to choose a successor to outgoing President Viktor Yushchenko.
Mr Yushchenko's time in office has been marked by strained relations with Moscow, and his departure was being seen as an opportunity for an improvement in ties between the two countries.
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