Side-chain liquid crystalline copolymers containing nitrobiphenyl were used to fabricate polar Langmuir multilayers. (Methoxyethoxy)methoxy terminal groups were incorporated in the copolymers to enhance the spreadability and monolayer formation of the copolymers. X-ray diffraction, second harmonic measurements, and pyroelectric studies all support the existence of a noncentrosymmetric structure for the polymeric multilayers. Thus, the possibility of using polymeric monolayers to prevent molecular turnaround upon X-type horizontal deposition was demonstrated. The molecular susceptibility for nitrobiphenyl was measured to be (9.8 +/- 1.0) X 10(-30) esu. The linear relationship between the square root of the second harmonic intensity (pp) and the number of layers (see Schemes I-V) indicates the good quality of the multilayers. The copolymeric multilayers with shorter spacers (see Schemes I-V) were found to have a lower second harmonic response. An unusual pyroelectric response was observed for Cop11 multilayers. The pyroelectric coefficients were determined to be 2.85 X 10(-10) C cm-2 degrees-C-1 for Cop11 and 2.0 X 10(-10) C cm-2 degrees-C-1 for Cop4. FTIR-RA studies show that the aromatic rings of Cop4 and Cop11 multilayers stay oriented in liquid crystalline phases.