After touring Beijing's sprawling Forbidden City, Macron met with Chinese business leaders and held talks with top officials at the imposing Great Hall of the People.
Xi, who had already hosted Macron and his wife Brigitte for dinner last night, treated the French leader to a military honour guard at the hall before their meeting.
Macron, who has positioned himself as the leading voice of the European Union, came to Beijing to discuss an ambitious agenda with Xi, the most powerful Chinese leader in decades.
Macron has put on the charm during the visit, giving Xi a Republican Guard horse as a gift and delighting Chinese social media users by releasing a video of him learning to say his climate slogan, "Make the planet great again", in Mandarin.
France, which runs a $30 billion euro ($ 36 billion) deficit with China, wants to "rebalance" its trade relationship with Beijing and, like other European nations, has demanded reciprocal access to the huge Chinese market.
"China is conducting its economic development strategy and, given the size of this market, it has an impact on globalisation as a whole," Macron said while visiting a startup incubator, which offers new companies office space and other services, in Beijing.
The two presidents are expected to oversee the signing of some 50 agreements, including in the strategically key sectors of nuclear energy and aviation.
Macron came to China with some 50 business leaders, including the heads of European aerospace giant Airbus and French state nuclear energy company Areva.
Ahead of the ceremony, Chinese online retailer JD.com announced plans to sell French goods worth two billion euros ($ 2.4 billion) to Chinese consumers over the next two years - including high-end wine and cognac - and spend 100 million euros on French industrial products.
In a keynote speech yesterday, Macron urged the EU to participate in Xi's cherished $1 trillion Silk Road trade infrastructure project despite misgivings, though he warned that the initiative should not create a "new hegemony".
It is the first state visit by a European leader since China's Communist Party congress in October, which reinforced Xi's grip on power as he was formally handed a second term and his name was enshrined in the party's constitution.
Beijing has praised Macron's decision to make China his first state visit to an Asian nation. US President Donald Trump visited the Chinese capital in November and was given a lavish welcome.
Earlier, Macron and his wife Brigitte were accompanied by students from the French international school and a French historian as they walked along the red-walled palaces of former Chinese emperors at the Forbidden City.
On a sunny but bitterly cold day, Macron asked historian Patrice Fava to translate a banner which read "With fairness, govern from the centre".
"It's important. It's symbolic," said Brigitte Macron, whose husband campaigned as a centrist candidate in the French presidential election.
At the Forbidden City's pavilion of Supreme Harmony, Macron drew a parallel with the 19th Communist Party congress.
"This also allows us to better understand one of the themes of the 19th Congress raised by President Xi Jinping," Macron said. "This also comes from a profoundly anchored history in this country.