Hollande, making his first visit to Russia since being elected president in May, will seek to reconcile France's vision of a post-Assad Syria with Moscow's insistence that only Syrians can decide their destiny.
Accompanied by his partner Valerie Trierweiler, Hollande will also be looking to find the same personal chemistry with Putin that existed with his predecessor and vanquished rival Nicolas Sarkozy.
Asked In a press conference on Thursday whether the two leaders would discuss French actor Gerard Depardieu, now a proud resident of Russia, Hollande said: "There is one thing certain with President Putin and that is we will talk about everything."
The French president also attempted to make light of the Depardieu furore, without specifically naming the now infamous French tax-exile.
When asked about giving French visas to Russian investors Hollande said: "We must limit immigration but that should not discourage a Russian investor or an entrepreneur, even artists or other famous people from coming to France.
"We don't stop anyone from coming to Russia," Hollande said to much laughter.
Syria top of the agenda
In a radio interview early Thursday, Hollande said he intended to discuss political transition in Syria with Putin and voiced cautious optimism that the leaders could bring their opposing positions closer.
"We will discuss this question and I hope Putin and I will manage to have a dialogue about the transfer of power," Hollande told Echo of Moscow radio station in comments translated into Russian.
France has been one of the strongest international backers of urgent action to bring about a power transfer in Syria that excludes Assad and can end a two-year conflict that according to the United Nations has claimed 70,000 lives.
Russia has denied it has a policy of propping up Assad, a long-term ally, but has not backed calls for him to stand down, saying this must be the Syrians' decision.
Taking a conciliatory approach, Hollande stressed his willingness to find a common language with Putin, whom he described as frank, while acknowledging that Putin would not back his call for Assad to stand down.
"When (Putin) says something, he says it honestly and it is his position," Hollande said. "That is President Putin… We do not yet share one position but it is changing and should come to a consensus decision."
The two men have met once before in Paris in June last year when their differences on the Syria conflict were laid bare in a press conference after the talks.
Hollande stressed Russia's key role as a member of the United Nations Security Council, where it has vetoed resolutions that would have put pressure on Assad to end hostilities.
"A lot will depend on the position of President Putin and on our position too, of course. We must finally start the process of political dialogue that has not yet started on the territory of Syria."
"President Putin and I both understand all the seriousness of the situation. And even though our positions at the moment differ, we want to find the best solution for Syria."
Hollande expressed optimism that international powers would find apolitical solution to stop the raging conflict from spiralling in the coming weeks.
"I think that in the next few weeks we will manage to find a political solution that will stop the conflict from escalating," he said.
Hollande spoke before a Friends of Syria meeting of foreign ministers wasto begin in Rome and United States Secretary of State John Kerry met Syrian National Coalition chief Ahmed Moaz al-Khatib to discuss greater aid for the rebels.
France has led moves to have the opposition Syrian National Coalition recognized internationally as the legitimate representative of the Syrian people.
On a mission to find common ground with Russia, Hollande said that he would bring up rights issues, without specifying, but added that he "would not like to use any provocative approach."
Human Rights Watch had urged the French leader in the run-up to the visit to press Putin on the rights situation in after the worst year for "human rights in Russia in recent memory."
Hollande also downplayed the fallout from Putin's decision to grant citizenship to French star Gerard Depardieu in a whirl of publicity after the actor rowed with the French authorities over high tax demands.
"I'm sure the Russian president made a choice that does not damage our interests," he said.