Nonlinear optical transmission of graphene oxide-(Cu, Zn, Sn, H 2) porphyrin composites was investigated using the Z-scan technique at 532 nm with picosecond (ps) and 800 nm with femtosecond laser pulses. Pure porphyrins show saturable absorption (SA) in reverse saturable absorption (RSA) behaviour and graphene oxide shows complete RSA behaviour, observed in an open aperture Z-scan curve. Interestingly, composites have shown a switch-over from reverse RSA to SA and back to RSA behaviour, observed with variation of intensity towards the focus, due to strong two-photon absorption as well as excited state absorption in the ps regime. This switching behaviour was interpreted as due to long lifetimes and saturation of the excited states. This may find application in optical switching. © 2014 IOP Publishing Ltd.