Drawing Powerpuff Girl

Start by drawing an ellipse using elliptical shape tool.

Apply stroke using following settings.

Create a duplicate of this ellipse. Remove the effect and fill with black color.
Enable subtract from shape area at the top bar.
Using pen tool draw as shown in the images below.

Using pen tool draw the outer hair as shown.
Duplicate and place this shape on the both sides of the face.
Draw a circle for the eye.
Enable subtract from shape area at the top bar .Using pen tool draw as shown in the images below.
Fill this shape with white color.

Apply stroke using settings below.
Duplicate this layer remove the effect. Fill it with green color. Press Ctrl+T and squeeze from left slightly.
Select rounded rectangle tool. Adjust settings as shown.
Draw a rounded rectangle for the pupil of the eye.
Draw a white ellipse to complete the eye.
Select all eye layers. Duplicate and flip horizontally and place it for the other eye.
Draw lips using pen tool.
Draw upper body shape using pen tool as shown.
Draw arms using pen tool and apply stroke layer style.

 

Draw legs using pen tool and apply stroke layer style.
Add details to the legs.
Fill the background with pink color.
Using pen tool create a few triangular shapes over the background.
Change layer mode to overlay for these triangular shapes.