With 99.99% of ballots counted yesterday, Macron had 66.06% of the vote in the first ever election he has contested, far ahead of the nationalist Le Pen at 33.94%.
Overnight he appeared side-by-side with outgoing president Francois Hollande - his former mentor - at a commemoration of the end of World War II.
But he is inexperienced, has no political party and must fashion a working parliamentary majority after legislative elections next month.
In his victory speech, Macron vowed to "rebuild the relationship between Europe and the peoples that make it".
Valls said Tuesday he wanted to be a candidate for Macron's centrist movement in June's legislative elections.
Sylvie Goulard, a French deputy to the European Parliament, said Macron would make Berlin his first official visit, with perhaps a stop to see French troops stationed overseas as well.
Macron aims to ease France's famously rigid labor laws that he believes fuel unemployment and wants to improve education in deprived areas as well as increase welfare protection to the self-employed. The movement is to be renamed La Republique en Marche ("The Republic on the Move").
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Last December, Valls was replaced as prime minister by Bernard Cazeneuve, who in his previous role as interior minister had overseen France's reaction to jihadist attacks.
He will inherit a population anxious about the economic impact of globalization and changes to French identity caused by immigration.
The decisive result favoring Macron laid to rest the idea that Le Pen and her party might be gaining enough strength to surprise with an outlier victory, such as occurred with the vote favoring Brexit and the win by President Donald Trump in the United States.
"The old parties are dying or are already dead", Valls said.
In interviews on Monday, National Front officials said the party founded by her father would get a new name to try to draw in a broader spectrum of supporters.
The election underlined France's economic and geographical divisions, with Macron popular among more educated, middle-class voters in cities, but viewed with suspicion or hostility by blue-collar workers.
Webber said: "Adam's extremely clear writing and analysis impressed me immediately: his eye for human detail and careful examination of the stages of the Macron surge add a thrilling dimension to this tale of unexpected political victory".