The 1937 "Femme au Beret et a la Robe Quadrillee (Marie-Therese Walter)" is expected to reach $50 million (€40 million) at a sale of Impressionist, Surrealist and Modern Art at prestigious London auction house Sotheby's on Wednesday.
The identity of its current owner remains a mystery.
"It's an incredibly important museum quality picture," James Mackie, director of the Impressionist and Modern Art department at Sotheby's, told AFP on Thursday.
"It comes from a key era in Picasso's career, 1937, when he makes the great painting 'Guernica'," he added, referring to the masterpiece which portrayed the horrors of the Nazi bombardment of a Basque city during the Spanish civil war.
The painting also has a strong autobiographical appeal, said Mackie.
The main subject of the piece, Marie-Therese Walter, was the Spanish painter's "long time lover and muse".
But the looming figure of Dora Maar, whom he met in 1936, emerges in the shadows behind Marie-Therese, explained Mackie.
Several masterpieces have reached astronomical prices at recent auctions, fuelled by the opening of major museums in the Gulf and the purchasing power of collectors from emerging countries.
Crown Prince of Saudi Arabia Mohammed bin Salman, acquired Leonardo da Vinci work "Salvator Mundi" for $450 million in November 2017.
"The market for masterpieces is at an unprecedented levels, and this picture certainly sits very much in that masterpiece category," said Mackie.
Three other Picasso works will be auctioned, including "El Matador", valued at between £14 and £18 million ($20-$25 million, 16-20 million euros).
Two Salvador Dali paintings are also up for sale.
Salvador Dali's, Maison pour Erotomane. Photo: Sotheby's
The two small oil works, "Gradiva" (1931) and "Maison pour Erotomane" (circa 1932), have been in a private collection in Argentina, having been bought directly from the artist by an Argentinean countess.
"They are a rediscovery, which is incredibly exciting," Mackie said of the two works.
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