Time-of-flight secondary ion mass spectrometry (TOF SIMS) and X-ray photoelectron spectroscopy (XPS) have been jointly used to study a two-step surface processing of AS4 carbon fiber: extraction of sizing in CH2Cl2 and functionalization with trimellitic anhydride. The combined information on molecular specificity obtained with TOF SIMS and quantification obtained with XPS allows us to follow qualitatively and quantitatively the changes in functional groups on the carbon surface. The results show that the sizing on AS4 contains at least four different compounds. These compounds can be extracted in CH2Cl2 and the elimination is almost complete for silicone. The functionalization of AS4 with trimellitic anhydride has been realized. The reaction takes place between the amine groups on the carbon fiber and the two types of functional groups in trimellitic anhydride.