The high-level diplomacy reflects Europe's mounting concern over the US administration's overtures towards Moscow after the failure so far of Trump's efforts to arrange a ceasefire in the three-year-old Russia-Ukraine war.
The US officials were also due to discuss nuclear talks with Iran during their visit to Paris.
Trump, who has long said he aims to swiftly end the Ukraine war, has indicated he is frustrated with both Moscow and Kyiv, even as his administration has shifted US rhetoric towards accommodating the Russian account of the conflict.
Ukraine agreed to a Trump proposal in March for a ceasefire that Russia rejected.
The sides have agreed only to curbs on attacks against energy targets and at sea, which both accuse each other of violating.
Kyiv and its European allies say Moscow is to blame for rejecting Trump's proposal of a ceasefire last month, and are hoping to persuade Washington to take a tougher line.
They have pressed the case since a Russian attack that killed civilians including Ukrainian Christian worshippers in the city of Sumy on Sunday.
"I'm just trying to get it stopped so that we can save a lot of lives," Trump said of the war on Sunday.
The arrival of a Ukrainian delegation in Paris on Thursday was not previously announced before what Washington had described as planned talks between Rubio, Witkoff and French officials.
President Volodymyr Zelenskiy's chief of staff, Andriy Yerma, said his delegation, which also included Ukraine's foreign minister and defence minister, would meet a US delegation as well as French, British and German officials, without specifying whether they would meet either Rubio or Witkoff.
"We are working on important issues for the security of Ukraine and the whole of Europe," Yermak said on X.
Ukrainian Foreign Minister Andrii Sybiha said: "The parties will discuss ways to achieve a complete ceasefire, the involvement of a multinational military contingent to guarantee sustainable peace, further development of Ukraine's security architecture and ensuring the security of our country."
German Chancellor Olaf Scholz's foreign policy adviser Jens Ploetner will also be in Paris for the meetings.
The talks come after a Russian mass drone attack killed three people, including a child, and injured many more on Wednesday evening in the southeastern Ukrainian city of Dnipro, the regional governor said.
Serhiy Lysak, governor of Dnipropetrovsk region, wrote on Telegram that a young woman and an elderly woman had been killed.
Lysak said 16 people had been injured, including three children.
As well as discussing the war in Ukraine, US and French officials said they would also discuss Washington's efforts to reach a nuclear deal with Iran.
Witkoff plans to fly on to Rome for a second round of discussions on Saturday with Iranian foreign minister Abbas Araghchi about Iran's nuclear program after they met last Saturday in Oman.
Both sides described last weekend's talks as positive while acknowledging that any potential deal remains distant.
Trump, who abandoned an earlier nuclear deal with Iran during his first term in 2018, said on Monday he was willing to bomb Iran's nuclear facilities if a new deal was not reached.
