I generally work loose when I start the character design process. At this stage, I'm focusing on form, proportion, and finding an overall silhouette that reads well - something that captures the essence of the character. The form should add visual information that captures the personality or nature of the character. Once I have a sketch that I feel will work well, I start working on Photoshop, my workflow is 100% digital, using a Graphic Tablet.
Sketch + Photoshop