A soluble graphite oxide (GO) axially substituted gallium phthalocyanine (PcGa) hybrid material (GO-PcGa) was for the first time synthesized by the reaction of tBu 4 PcGaCl with GO in anhydrous DMSO at 110• C in the presence of K 2 CO 3 . The formation of a Ga-O bond between PcGa and GO has been confirmed by x-ray photoelectron spectroscopy. In contrast to GO, the D and G bands of GO-PcGa in the Raman spectrum are shifted to the lower wavenumbers by ν = 11 and 18 cm −1 , respectively. At the same level of concentration of 0.1 g l −1 , GO-PcGa exhibit much larger nonlinear optical extinction coefficients and strong optical limiting performance than GO, tBu 4 PcGaCl and C 60 at both 532 and 1064 nm, implying a remarkable accumulation effect as a result of the covalent link between GO and PcGa. GO-PcGa possesses three main mechanisms for the nonlinear optical response-nonlinear light scattering, two-photon absorption and reverse saturable absorption for the 532 nm pulses and nonlinear light scattering for the 1064 nm pulses. tBu 4 PcGaCl does not make any significant contribution to the optical limiting at 1064 nm, while GO-PcGa has a much greater optical limiting response than GO at this wavelength, this suggesting that the PcGa moiety could certainly play an unknown but important role in the GO-PcGa material system.