Vector Tutorial

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Alrighty then. Assuming you know about the pen tool tutorial, we're going to start right away.
First off, make sure you have the following selected:

Now, open up your Samurai Champloo scan (or whatever scan you want to vector). Press Ctrl + Shift + N to make a new transparent layer above the "background" layer. Name it "outline". Next, make another layer and fill it with white. Place it below the "outline" layer. Click on the small eye next to "Layer 1" to make it invisible until it's needed.

Quick note: Please please please name all your layers! It's sooo much easier when you do!

Right. Now we can start the outline! For this scan, zoom in to about 200%.
Using the pen tool, and on my "outline" layer, make a starting point and an ending point:

Now to make a curve. In between your starting point and the last point you made, make another point:

Still using the pen tool! To make the actual curve, hold Ctrl and click on the middle point. Still holding Ctrl, drag the point to the left and, when you've chosen where you want it, let go of the point (and Ctrl). You can make multiple middle points to get the curve exactly as you like! It should look something like this: ( Note: I went a bit further to illustrate the curves.)