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George Washington (Lansdowne portrait), 1796 by Gilbert Stuart, National Portrait Gallery, Smithsonian.
This portrait of Washington was on loan to the Smithsonian for many years until the owner decided to sell it. It was offered to the NPG for $20 million. A gift was given that allowed for its purchase and to renovate the gallery where it hangs.
Throne of the Third Heaven of the Nations' Millennium General Assembly, c. 1950-64 by James Hampton, The Smithsonian.
James Hampton worked as a Janitor to earn a living all his life, on his off time he was compelled to create art to express his strong religious beliefs. He made this assemblage out of discarded furniture, flashbulbs, wrapped in gold and silver foil and purple tissue paper.
The Peacock Room, 1877 by James McNeill Whistler, Freer Gallery, Smithsonian.
Whistler, in his usual flamboyant and arrogant manner, took his decoration of this London dining room to such an extreme, he angered and the patron and made their argument public.
Landscape: A Man Looking at a Waterfall, Qing Dynasty (1644-1911), Freer and Sackler Galleries, Smithsonian.
The first time someone told me to look at Chinese paintings up and down instead of across, it made seeing the whole image so much easier.