The surface properties of polymers, copolymers, and polymer bends are very important to many industrial applications. Especially, the surface properties of copolymers and polymer blends can be very different from those of bulk. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been the two of the key surface analysis techniques that are widely used to characterize these surfaces. This review provides a brief introduction to the principles of XPS and ToF-SIMS and their applications to study of the surface of copolymers and polymer blends.