New Ukrainian representatives will be appointed to the Czech Republic, Germany, Hungary, Norway and India.
It comes after Ukrainian President Volodymyr Zelenskyy dismissed diplomats based in those countries, including his ambassador to Germany, Andriy Melnyk, according to a decree published by the presidential chancellery.
The decree did not state why, or what they would do in the future.
"Today, I signed decrees on the dismissal of some ambassadors of Ukraine," President Zelenskyy said.
"This rotation is a normal part of diplomatic practice. New representatives of Ukraine will be appointed to the Czech Republic, Germany, Hungary, Norway and India. Candidates are being prepared by the Ministry of Foreign Affairs," he said in a video message.
The Ukrainian embassy in Berlin did not comment on the decree.
"The Foreign Office has not yet been notified of the ambassador's dismissal," a spokeswoman for the Foreign Office said.
Andriy Melnyk became known for his repeated demands for more support from the German government, in the form of heavier weapons, as Russia's attacks continued in the war launched by Moscow on 24 February.
Recently, the former Ukrainian ambassador to Germany came under pressure for defending the Ukrainian nationalist leader Stepan Bandera, who led a group responsible for the deaths of tens of thousands of Poles and Jews during World War Two.
During an interview broadcast in Germany, Mr Melnyk said he disagreed with the "Russian narrative" on Mr Bandera, saying he is "not a mass murderer of Jews and Poles".
The Israeli embassy accused Mr Melnyk of "distorting historical facts, trivialising the Holocaust and insulting those who were murdered by Bandera and his people".
Mr Melnyk initially did not respond, but later rejected the accusation.
"Everyone who knows me, knows: I have always condemned the Holocaust in the strongest possible terms," he tweeted, calling the accusations "absurd."
Mr Melnyk has served as ambassador to Germany since January 2015, longer than diplomats usually remain in a post.
Commentators in Kyiv also noted that this was twice the usual posting time.
German Federal Parliament, or Bundestag, deputy head Katrin Göring-Eckardt expressed her respect for Mr Melnyk after news of his dismissal emerged.
"Andriy Melnyk has worked for his country with all his might. He is an unmistakable and tireless voice for a free Ukraine," the politician said.
However, she stressed that she disagreed with Mr Melnyk regarding Mr Bandera.
"Regardless, I wish him all the best personally, for his future service and above all for his country," Ms Göring-Eckardt said.
Some German media, including Bild and Süddeutsche Zeitung newspapers, reported that Mr Melnyk is to be moved to the Foreign Ministry in Kyiv, citing Ukrainian sources.
