On Sunday, Ukraine's Russian speaking southern peninsula of Crimea will hold a referendum where residents will vote on whether to break from the former Soviet country and join Russia - a move Hollande said has no legal basis in his telephone call with Putin.
However, the Russian take on the two leader's conversation took a very different tone with the Kremlin saying the two heads of state discussed ways to bolster international support as a solution to end the crisis in Ukraine.
Russian troops took control of Crimea shortly after Ukraine’s pro-Kremlin leader Viktor Yanukovych was ousted from office in February after months of heavy protests.
Hollande called for a withdrawal of Russian troops from the region their first military involvement in a neighbouring country since its brief 2008 war with Georgia and requested Russia to respect the "sovereignty and territorial integrity" of Ukraine.
The Group of Seven most developed economies, which includes France, also said on Wednesday that a Moscow-backed referendum in Crimea would flout international law and called on Russia to back down.
Russia has also said it will mirror any visa sanctions the European Union imposes on its lawmakers, according to senior parliamentarian Alexei Pouchko who spoke to Russian news agencies on Wednesday.
This could involve the freezing of interparilamentary relations and could stunt the work of international organisations like the Council of Europe and the OSCE.
Presidential elections are set to take place on 25 May in Ukraine, which Hollande says must be held under international supervision and with the "greatest transparency."
French foreign ministers are also set to visit Moscow on 18 March.
"It has been agreed to continue the discussion including during a visit to Moscow by the French foreign and defence ministers, planned for March 18," said a statement issued by the Kremlin following a telephone conversation between Hollande and Putin.