Yeah, writing simple C programs using various constructs (switch/if/for statements, structs, different APIs, etc.) and then looking at the produced assembly is a good way to learn.
Another thing I like to do is to rewrite complex parts of the disassembly in pseudo-C (though radare has an option to do this automatically), which makes the overall logic easier to see (and is, of course, the entire point of decompilers like Hex-Rays).
This works. Be sure to try different compilers and optimization levels.
You can become a better programmer this way. You start to get a real feel for what the compiler can and can't optimize. For example, you can see how a do...while loop is usually the best kind of loop, but without seeing the assembly you might assume they are all the same.
Another thing I like to do is to rewrite complex parts of the disassembly in pseudo-C (though radare has an option to do this automatically), which makes the overall logic easier to see (and is, of course, the entire point of decompilers like Hex-Rays).