The 6.3-billion-euro (USD 7-billion) agreement includes an order for 24 jets manufactured by French defence group Dassault with an option on a further 12 planes.
Hollande will meet Qatar's Emir Sheikh Tamim bin Hamad al- Thani before flying to Saudi Arabia to attend a key Gulf Cooperation Council summit there tomorrow - a first for a Western head of state.
He is set to discuss with Sheikh Tamim the several crises rocking the region, including the weeks-long Saudi-led coalition aerial campaign on anti-government rebels in Yemen.
In addition to Qatar and Saudi Arabia, the GCC includes Bahrain, Kuwait, Oman, and the United Arab Emirates.
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Having struggled for years to sell any of its Rafale jets abroad, Dassault has recently scored several lucrative, high- profile contracts with Egypt, India, and now Qatar.
Accompanied by Foreign Minister Laurent Fabius and Defence Minister Jean-Yves Le Drian, Hollande will attend a signing ceremony for the Rafale contract today.
A separate agreement will see France train 36 Qatari pilots and around 100 mechanical engineers, as well as intelligence officers. Rafale jets can be used for reconnaissance missions.
Le Drian, whose several previous trips to the Middle East have mostly been confidential, met yesterday with Abu Dhabi Crown Prince and UAE deputy armed forces chief Sheikh Mohammed bin Zayed al-Nahyan.
The pair discussed "mutual cooperation in military defence" including possible training deals, according to the official WAM news agency.