Leone (Akame ga Kill!) - Process

1, 2, ..., 12 from left to right.

1. Photoshop - Loose Sketch
2. Photoshop - Tighter Sketch
3. Painter - Clean Lineart
4. Photoshop - Flats.  I also put up a general light source for the character, since I didn't really plan on doing anything crazy with lighting for this.
5-7. Photoshop/Painter - Flipflop between programs for skin work. These always take me the longest to render.
6. Photoshop - Hair is done entirely in Photoshop, though I may start switching to Painter for this as well.  In the end it will probably depend on what style I'm going for.
9. Black Bikini(?) was done with a mix of Photoshop and Painter. The rest was done in Photoshop, since I'm still not as comfortable with rendering cloth in Painter (getting there).
Textures were done in Photoshop.
10-11. It's usually easier for me to just start out with a monochrome background, particularly for this kind.  Personally, I think my backgrounds are kind of "meh".  
12. Finished!  Leone (Akame ga Kill!)

Brushes: I mostly use ones that are already there in the programs. Any "custom" brushes I use can be found in my Favorites gallery.  Remember, though, they're just tools; it's up to you on how you use them.

Layers: For this one, if you saw the layer organization, you'd probably get lost at first glance, but there's a hierarchy to my setup.  At the very least, I did keep the main flats on separate layers.  It helps for making some quick edits.  You can make your layer organization as complex as you want, provided you can still follow it and not get lost.  Other times I just leave all the flats on one layer and just Magic Wand half the time.  Again, it just really depends on what you're going for and what you think is the best workflow for what you're working on.

Resolution: I work in 300dpi, as most other people do, unless it's something tiny, like forum avatar.  This one was 2700x3600, but I've recently gotten accustomed to around 4000x5000.