If it's in a gif formatt, and not in layers, you'll need to mask and remove the background- use the wand tool and the lasso tools to select the pixels you wish to remove, then edit>mask>hidemask, or reveal mask (dependant on if you selected the image you want to keep, or the colours you want to remove)
Save the image with a transparent background.
(you may need to clean up the image, and make sure you work on a copy of the image, so you can try out differnt settings- I tend to use anti aliais, or feather at 1 to keep the edges smoother)
Sometimes, when my code just won't behave, I take it outside and make it listen to britney spears music, and when it comes back it's really well behaved. I wonder if it's suffering from post tramatic stress syndrome now..