We demonstrate a method for the realization of highly nonlinear optical 4-(4-dimethylaminostyryl)- 1-methylpyridinium tosylate (DAST) two-dimensional structures by a double-step technique. The desired polymeric structures were first fabricated by using the multiple exposure of the two-beam interference technique, and the DAST nanoscrystals were then prepared inside the air-voids of these photoresist templates, resulting in nonlinear periodic structures. The nonlinear properties were characterized by optical and scanning microscopies, as well as by second-harmonic generation technique. This nonlinear modulation is very promising for the enhancement of nonlinear conversion rates, such as terahertz generation, by using the quasi-phase matching technique.