For the first time, second-harmonic generation microscopy (SHGM) has been employed to study zeolites. Large ZSM-5 crystals filled with p-nitroaniline (PNA) dipoles have been visualized. It is shown that SHGM can discriminate between the straight b-pores and the sinusoidal a-pores of this zeolite, thus revealing the intergrown structure of these crystals. Moreover, it is shown that dipole chains are formed not only in the b-pores but also in the a-pores. PNA only assembles into dipole chains of parallel orientation in those pores that are directly accessible from the outer surface. The area in which this PNA ordering prevails is limited to a strip near the outer surface of the zeolite crystal. A rationalization for these two observations is offered.