The nonlinear absorption (NLA) properties of copper phthalocyanine (CuPc)-doped polymethylmethacrylate (PMMA) thin film in the femtosecond regime were investigated both experimentally and theoretically. The open-aperture (OA) Z-scan measurements of the film were carried out by femtosecond laser pulse. A transition from saturable absorption (SA) to reverse saturable absorption (RSA) was observed as the excitation intensity is increased. The rate equation analysis based on an developed efficient energy level model was performed and the intensity dependence of level populations was obtained, which reveals the source of NLA. The results show that the transition from SA to RSA is ascribed to the fifth-order effect of excited-state absorption (ESA) induced by two-photon absorption (TPA) process. Furthermore, it is found that the CuPc-doped PMMA thin film possesses a large fifth-order coefficient (beta((5))) of 0.24 x 10(-21)cm(3)/W(2). It indicates that the CuPc-doped PMMA thin film could be a promising candidate for optical limiting material.