You can create a new image with the desired new size, and paste the old image in the center, then saving it. If you want, you can overwrite the original image (are you sure? ;o)
import Image
old_im = Image.open('someimage.jpg')
old_size = old_im.size
new_size = (800, 800)
new_im = Image.new("RGB", new_size) ## luckily, this is already black!
box = tuple((n - o) // 2 for n, o in zip(new_size, old_size))
new_im.paste(old_im, box)
new_im.show()
# new_im.save('someimage.jpg')
You can also set the color of the new border with a third argument of Image.new()
(for example: Image.new("RGB", new_size, "White")
)