An electron transfer between Fe(III) of Mg-Fe(III) LDH (Layered Double Hydroxide) and Co(II)TPPS (cobalt(II)-tetraphenylporphine tetrasulfonate) as the guest was investigated. With a low coverage of the guest, the electron transfer occurred during the adsorption process to form an intercalation hybrid. On the other hand, light irradiation (>400 nm) of the hybrid powder resulted in a reverse electron transfer to Co(II)TPPS/Mg-Fe(III) LDH. Structural changes in the laminating hybrid were observed to take place concurrently with the electron transfers.