Witkoff, who recently met with Russian President Vladimir Putin, and Rubio are heading to Paris for talks on ending the war in Ukraine, the State Department said separately.
US President Donald Trump's push for a ceasefire in Ukraine has yet to bear fruit despite his pledges to end the war quickly.
Russia's strikes that have recently killed dozens of people including many many children in Ukraine's cities of Sumy and Kryvyi Rig show how the war is taking a hefty toll despite a series of diplomatic efforts.
Macron has taken the lead in seeking to forge a coordinated European response to protecting Ukraine, both during the current conflict and in its eventual aftermath after Trump shook the world by opening direct negotiations with Russia.
The State Department said Rubio was travelling with Witkoff to meet European officials for talks on the goal of stopping the war triggered by Russia's invasion in 2022.
A French diplomatic source said Rubio and France's Foreign Minister Jean-Noel Barrot would discuss "the war in Ukraine, the situation in the Middle East and the Iranian nuclear file".
This will be Rubio's third trip to Europe since taking office.
Witkoff said on Monday, just days after his third meeting with Putin, that he himself sees a peace deal "emerging".
Talks to end the Gaza war have also stalled, with Israel saying on Wednesday it would keep blocking humanitarian aid from entering the Palestinian territory, where a relentless military offensive has turned the Palestinian territory into a "mass grave", according to medical charity Doctors Without Borders.
Israeli Defence Minister Israel Katz said blocking aid to the besieged territory of 2.4 million people was to pressure the Palestinian militant group Hamas.
The Paris talks also come after discussions between the United States and Iran on Tehran's nuclear program were held Saturday in Oman.
Another round is scheduled for April 19, also in Oman.
Separately, the French defence minister, Sebastien Lecornu, will travel to Washington on Thursday.
He is set to meet with Pete Hegseth, US Defense Secretary, for talks on a number of issues including Ukraine, Iran and Gaza.
He was also expected to hold talks with National Intelligence director Tulsi Gabbard and Keith Kellogg, Trump's Ukraine envoy.
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