I’ve been making Vector Art for a while (since 2004). You can find all my drawings on my Deviant Art.
Vector Art consists in drawing lines, not with pixels like in a regular picture, but with vectors: 2 points with 2 curve tangent. You work with coordinates and tangent which means that you can resize or zoom in the picture anyway you want without quality loss. You can also edit the lines at anytime with precision and play with layers, transparency, textures without limit. I’m using Paintshop Pro 8 (2003) which is getting a bit old but I still manage to do everything I want with it. I tried newer versions but they felt really heavy and slow so I went back to Pro 8.
I must say that I’m not very good at drawing with a pen, I actually have 0 drawing skills. I do everything with my mouse, I start with a raw sketch representing the basic pose and then I spend days/weeks trying to make it look nice with small details that create the illusion of volume.
I added some captures from the raw vector files and an animated gif that shows the evolution of the drawings as I was making them.