Synthesis and measurements of third order nonlinear optical (NLO) coefficients of water soluble zinc octacarboxy phthalocyanine (ZnOCPc) are reported here using different laser pulse durations. Nonlinear absorption and refraction behaviour in the nanosecond (ns), picosecond (ps) and femtosecond (fs) time domains were studied in detail. Three-photon absorption was the prevalent mechanism with femtosecond laser excitation whereas strong reverse saturable absorption due to dominant two-photon absorption (TPA) was observed with picosecond and nanosecond excitations. We have evaluated the sign and magnitude of the third order nonlinearity in fs, ps, and ns regimes. We observed large off-resonant second order hyperpolarizability (γ) with ultrafast nonlinear optical response in the femtosecond domain using degenerate four wave mixing (DFWM) technique. We also report the optical limiting characteristics and figure of merit (FOM) of ZnOCPc for optical switching. © 2012 World Scientific Publishing Company.