Appropriate amount doping of fullerenes caused insulating phosphate and fluorophosphate optical glasses to be conductive at room temperature. Microphotoluminescence measurements indicated the existence of ordered and disordered microstructures. A large number of fullerene-related medium-range microdomains aggregated as self-organized islands along the glass networks, and brought about connective tissues in the vitreous matrices for percolation migration of metal cations. The variation of microphotoluminescence induced by electric field presented us an indirect way to characterize the random activation, percolation migration, and retrap of metal cations near fullerene-related amorphous islands.