GNP-LC hybrid incorporating giant gold nanoclusters was accessed with tailor made liquid crystalline Schiff base bearing amine function as reactive end group without using any external reducing agent. The liquid crystal phase (smectic C) of the Schiff base remained unaltered in the hybrid material. The ligand and hybrid both exhibited interesting concentration-dependent fluorescence quenching of 9,10-diphenylanthracene when excited at 345 nm wavelength in dichloromethane solution. The GNP-LC hybrid exhibited reasonably good electrical conductivity showing an Arrhenius-type behaviour in the smectic mesophase and a tunnelling behaviour in the crystalline state.