This is a detail from the Rogue litho I just finished for Sideshow Collectibles; it comes with the Rogue comiquette if you order the exclusive version. I just posted the whole image a few moments ago.
Since my hand is messed up, I couldn't pencil and ink this the way I'd like. So, since I needed to make sexy lemonade out of this mess, I took my original concept illustration and just colored & painted it in Photoshop.
Before anyone asks, here's the reasons why I cropped it... First, I thought that the Black Cat print was dull, and one of the reasons is because it's full figure. You don't NEED a full-figure print of the character.... because you have the statue! You can see her toes THERE. I decided to crop in so that the piece would be about the face and the body language. I also cropped in because time was tight, San Diego was looming, and the AC was out and it was 95 degrees in my house.
As for technique/method.... I took the original high-rez Grayscale scan, cropped it, and converted it to CMYK Mode. It looked the same. I then used things like Variations, CHannel Mixer, and Hue/Saturation to change the gray values to have hues. At that stage, it looked like an oil painter's underpainting.
I then went in and built up the highlights using the pencil tool set on 10-21% opacity to slowly build up my "brush strokes" and give it an analog feel.
The highlights on the latex were accomplished using the lasso tool and my color Fills set to Screen or Linear Dodge.