Familiarize yourself with using the path tangent handles to control curvature instead of just drawing linear segments.
You know I would have said that was done with the lassoo tool if the OP had not specifically mentioned the Pen tool.
Anyway young Scribor2, all is not lost. With the Pen tool selected, hover one of the point on your work path. If no points are visible, hold down the Ctrl (Cmd) key and drag a window across any corner, which will make the points appear. Now release the Ctrl (Cmd) key, hover directly over a point, and hold down the Alt (Opt) key. The cursor will change to the 'Convert Corner' icon, so just drag, which will cause the handles mentioned in the above post to appear. You'll have no trouble working it out from there.
Much appreciated Trevor. Now I have questions regarding drawing things in Photoshop. If you were given a task to create super mario how would you do it. Would you trace it like i did with Bezier or would you make selections on image (say hat) and then copy it into another layer? How would you do it?
Reason I ask is because I am seriously "disadvantaged" for any drawing by hand and therefore I am assuming in Photoshop as well.
If you want to make a pen or pencil line drawing of an existing image you can:
Image>Adjustment>Desaturate then (same route)>Invert
Then use Levels and Selective Colour to remove greys you don't want or darken greys you do want.