The first photograph of a sitting United States president was taken of William Henry Harrison on March 4, 1841. The new executive had just delivered his inaugural speech -- the outdoor address now most remembered (wrongly) for giving him the pneumonia that would kill him -- and he paused, afterward, to pose for a portrait using the new technology of the daguerrotype.
That photograph, much like its subject, had an unexpectedly short tenure. Harrison's inaugural portrait has since been lost to history -- meaning that the oldest surviving photograph we have of an American president depicts a chief executive after his presidency. There are a couple candidates for "oldest." But they are, regardless, depictions of John Quincy Adams, the sixth president, in office from 1825-1829.
One is this, a sixth-plate daguerrotype made of the ex-president at the age of 76:
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