The laser induced etching of semi-insulating GaAs 〈100〉 is carried out to create porous structure under super-and sub-bandgap photon illumination (hν). The etching mechanism is different for these separate illuminations where defect states play the key role in making distinction between these two processes. Separate models are proposed for both the cases to explain the etching efficiency. It is observed that under sub-bandgap photon illumination the etching process starts vigorously through the mediation of intermediate defect states. The defect states initiate the pits formation and subsequently pore propagation occurs due to asymmetric electric field in the pore. Formation of GaAs nanostructures is observed using scanning electron (SEM) and atomic force microscopy (AFM).