Yes, you can cast polymorph on a familiar from find familiar.
The description of the polymorph spell simply says it targets a creature:
This spell transforms a creature that you can see within range into a new form. [...] The spell has no effect on a shapechanger or a creature with 0 hit points.
[...] The new form can be any beast whose challenge rating is equal to or less than the target's (or the target's level, if it doesn't have a challenge rating).
As noted in the official ruling on whether a familiar counts as an ally for Sneak Attack, a familiar is a creature.
The description of the find familiar spell says:
You gain the service of a familiar, a spirit that takes an animal form you choose: bat, cat, crab, frog (toad), hawk, lizard, octopus, owl, poisonous snake, fish (quipper), rat, raven, sea horse, spider, or weasel. Appearing in an unoccupied space within range, the familiar has the statistics of the chosen form, [...]
The CR of a familiar from the spell is, in fact, that of the chosen form.
A familiar is not considered a shapechanger just because it's a spirit that takes an animal form. A creature that is considered a shapechanger will have that monster tag appear in parentheses following its type (as seen in the doppelganger's statblock).
Note: A familiar still cannot attack even in its new form, as it is still a familiar. Per the spell description:
[...] A familiar can't attack, but it can take other actions as normal.
Note 2: If you dismiss your familiar or it is reduced to 0 hp, and then you resummon it, the familiar is brought back in one of its original forms, and not in the form you chose with the polymorph spell.