Two organic−inorganic hybrids, [3-H 2 DPNDI]-[ZnCl 4 ]•0.5H 2 O (1) and [4-H 2 DPNDI][ZnCl 4 ]•0.5H 2 O (2) (3-H 2 DPNDI 2+ = protonated N,N-di(3-pyridyl)-1,4,5,8-naphthalene diimide, 4-H 2 DPNDI 2+ = protonated N,N-di(4-pyridyl)-1,4,5,8naphthalene diimide), have been designed and prepared. Compounds 1 and 2 are constructed from typical [ZnCl 4 ] 2− inorganic clusters and positional isomeric organic cations of [H 2 DPNDI] 2+ , which are assembled into different three-dimensional supramolecular networks via different anion-π interactions and hydrogen-bonding interactions. Photochromism of 1 and nonphotochromism of 2 are attributable to the usage of positional isomers, which leads to the different spatial stack of [ZnCl 4 ] 2− donors and [H 2 DPNDI] 2+ acceptors, suggesting a delicate modulating effect of the distinct interfacial contacts on the intermolecular charge transfer/electron transfer and consequently photoresponsive behaviors.