Called "The Guggenheim Collection", highlights from the Guggenheim Foundation’s worldwide trove, is expected to attract at least 600,000 visitors.
Vasily Kandinsky's "Composition 8" faces Pablo Picasso's "Woman with Yellow Hair," while Andy Warhol's "150 Multicolored Marilyns" stare at Roy Lichtenstein's "Interior with Mirrored Wall."
Pieces from Guggenheim museums in New York, Bilbao, Venice and Berlin are being displayed together for the first time.
Artists range from ranges from Edouard Manet and Marc Chagall to Paul Auguste Renoir, Jackson Pollock and Mark Rothko.
"We wanted to show the enormous extent of the Guggenheim collection," Susanne Kleine, the Bonn-based curator, said.
The scale of the show is such that it is spread across the Art and Exhibition Hall and the Kunstmuseum Bonn – but it still only features 4% of the foundation’s total works.
"The great concept of this show gives you a thorough overview of various art periods and artists," said one early visitor.
The show follows previous collaborations by the Art and Exhibition Hall with New York's Museum of Modern Art of New York, in 1992, and the Tokyo National Museum, in 2003.
The visitor's walk starts with some of the first Kandinsky works bought by Solomon R. Guggenheim, the founder of the collection.
Focusing mainly on painting, the exhibition moves from the emotionally inspired expressionist period to playful surrealist works by Max Ernst and Salvador Dali.
A staircase constructed for the exhibit offers a panoramic view of huge, minimalist installations by Bruce Nauman and Carl Andre.
Pop Art works round off the display with Lichtenstein's image of a growling dog leading the way to the exit.
Next door at the Kunstmuseum, the "Guggenheim Contemporary" exhibit includes works by such figures as Rachel Whiteread or Roni Horn.
Massive installations include Matthew Ritchie's "The Hierarchy Problem," which consists of a canvas, paintings on the floor and the wall, a sculpture and a light box, spread through an entire room.
The exhibition runs until January 7.