In the live-action film that came out in 2005, Dr. Doom formerly
owner of an American company; later dictator of the European nation
of Latveria, with a body that took on properties of metal and the
ability to manipulate electricity.
In a somewhat different form for the comics series(far more
serious and far less hokey), he has also been a major villain not
only for the Fantastic Four but the Marvel Universe as a whole;
being portrayed as sometimes working alongside the heroes in order
to achieve his ends, he is a far more complex character than the
film version.
Otherwise, there are hundreds of "villains" from the Fantastic
Four series.
The villain for the second film was Galactus.