He's actually switching between photoshop and Deep Paint 3D, one of its features is projection mapping, which is what he's using in the tutorial. the program is pretty old and i'm not sure if it works with windows 8 http://www.righthemisphere.com/products/dp3d/Deep3D_UV/index.html though i'm sure there are modern equivalents, i'll look into it when it's not past 1am
edit: actually i lied, found something. looks like this zbrush plugin does about the same thing as Deep Paint 3D http://www.pixologic.com/blog/2010/10/zapplink-for-zbrush-4-is-now-available/
edit: i have confirmed that it does, indeed, do exactly the same thing