**Yes!** Absolutely, characters can learn more than one kind of alchemy. It's just that, as in real life, people tend to specialize in something very specific and get *very* good at it.

But let's take a look at a few examples:

- **Edward Elric:** Like Alphonse, he takes after Izumi Curtis's style (including the big fists and such), but was able to attempt Human Transmutation, soul binding, modification of object structures (such as what he did in Youswell or in Greed), and even weird, quirky things like transforming a military vehicle into a clown car.
- **Roy Mustang:** Specializes in flame alchemy, but is seen, most obviously at the end of the series, to be able to modify structures of objects (when he makes a wall out of the ground). To do this prior to his "accident", he would have had to draw the transmutation circle, which is obviously less effective.
- **Tim Marcoh:** Specializes in medicinal alchemy, but did so even before he began to specialize in the creation and destruction of Philosopher's Stones.
- **Scar:** Is able to perform both destruction and creation alchemy through different transmutation arrays.

Then there's a few oddballs, but the rule can still apply to them:

- **Van Hohenheim:** Specializes in medicinal alchemy, but is also seen modifying object structures including metal and stone.
- **Father:** Can do pretty much everything, even before the climax; he is able to make homunculi, reshape metal, etc.

Keep in mind that, similar to what [@kaine](http://anime.stackexchange.com/users/3561/kaine) said, transmutation circles come into play. Not just in knowledge, though; the person actually has to either have that transmutation circle with them or draw it on the spot, which is not feasible in combat. So, someone like Armstrong would not thrive at the same things as Basque Grand, because they both use different transmutation circles. This is clear with Mustang who broadens his use of alchemy after his "accident".

So from this, we can tell that it's possible for alchemists to learn more than one type of alchemy, but it's difficult for them to always apply it under pressure (for multiple reasons); given cases like Ed, who doesn't need transmutation circles, we can see a broader range of alchemy used.