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There seems to be a certain consensus among stamp collectors that the first art stamp was the Canadian 1851-issue of Queen Victoria, based on Edward Alfred Chalon's (1780-1860) painting of the queen 1838.
According to Canadian Postal Archives it is the first definitive stamp showing the portrait of monarch, based on a painting.
Canada 1851. Queen Victoria, 12d, based on a painting by Alfred Edward Chalon "Queen Victoria", 1837. Scan by courtesy of Hans-Martin Leth.