The summit in Paris will mark the first time Russia's Vladimir Putin meets face-to-face with Ukraine's new comedian-turned-president, Volodymyr Zelensky.
Few are expecting an immediate breakthrough, but Zelensky's election this year and a recent easing of tensions have raised hopes of resolving the five-year conflict.
French President Emmanuel Macron, who will mediate along with German Chancellor Angela Merkel, pushed hard for the talks and they will be a test of his efforts to reset Europe's ties with Moscow.
Speaking to reporters in Kiev this week, Zelensky played down expectations but said it was "very important" the summit was taking place at all.
"Honestly, I don't know whether we will succeed or not, but the first victory is that we are meeting," he said.
Since it broke out in 2014, the conflict between Kiev and Russia-backed separatists in eastern Ukraine has killed more than 13,000 people, forced more than a million from their homes and battered the country's economy.
It has also deeply strained ties between Russia and the West, with the United States and European Union imposing sweeping sanctions on Moscow over its annexation of Crimea and support for the separatists.
Monday's talks will be the first in three years under the so-called Normandy format, which aims to put in place accords agreed in Minsk by Russia, Ukraine, France and Germany in February 2015.
The Minsk accords called for a ceasefire, the withdrawal of heavy weapons, the restoration of Kiev's control over its borders, the granting of wider autonomy to separatist-controlled territory and the holding of local elections
But the deal was never implemented and talks stalled under Zelensky's predecessor Petro Poroshenko.
Since coming to power in May after a shock election win, Zelensky has overseen a series of steps to reduce tensions, including a historic exchange of 70 prisoners with Russia, the withdrawal of some frontline forces and the return of Ukrainian ships seized by Moscow last year.
The Kremlin has sent signals that it is ready to work with Zelensky, who Putin has described as "likeable" and "sincere".
Zelensky has said he will be pushing on three points at the talks: another exchange of prisoners -- preferably before the New Year, the implementation of a ceasefire and the disbanding of all "illegal" armed groups on Ukrainian territory.
Putin has been less forthcoming about his intentions, but Moscow will likely seek guarantees on the status of the separatist-held territories of Donetsk and Lugansk and the conduct of elections.
The Russian leader will also be looking to hear from France and Germany about the possibility of easing sanctions that have hit his country's economy.
The issue of Russian gas transiting through Ukraine to Europe might come up as well, ahead of a late December deadline to avoid a cut off.
'Change in the mood music'
Zelensky will have to tread carefully. Led by nationalists and war veterans, a series of protests have broken out in Kiev in recent weeks warning against any "capitulation" to Russia.
And he may have lost a key ally in the United States, as longstanding bipartisan American support for Kiev is called into question by Donald Trump's impeachment scandal.
Macron will be anxious for progress in the negotiations, having spearheaded a drive for the talks and launched an effort to reopen a dialogue with Moscow.
He first mooted a summit at a meeting with Putin in the south of France in August and has since spoken repeatedly with the Russian leader by phone.
Mark Galeotti, an associate fellow with RUSI in London, said it was unlikely there would be concrete progress at the talks, but that they were nonetheless crucial.
"It's important because it represents potential for a change in the mood music, it's a first step," Galeotti said.
"The Russians are actually making quite a lot of noises suggesting they are much more willing to negotiate than in the past... There has been a meaningful shift."