Nonlinear optical (NLO) ultrathin films of a preforrned asymmetric polydiacetylene have been fabricated by Z-type Langmuir-Blodgett film deposition from the air-water interface. Induced in-plane orientation of the polydiacetylene backbone on the substrates has been confirmed by UV/Vis, FT-IR dichroism, and degenerate four wave mixing (DFWM) studies. All the measurements indicate that the backbone is prefe rentially oriented along the dipping direction. Second harmonic generation study suggests that the LB multilayers form an asymmetric structure (Z-type) due to the accumulation of 2-dimensional ordered monolayer and the dominant induced second order polarization is in the plane of the film. The film morphology and molecular orientation have been investigated by atomic force microscopy (AFM).