A side-chain liquid crystalline copolymer containing ether-nitrobiphenyl groups was investigated as a nonlinear optical material. Ultrathin films have shown second harmonic generation and therefore have a variety of interesting applications. Waveguides composed of multilayers of the copolymer have been fabricated, and propagation losses as low as 2.3 dB/cm in a lowest order TE mode at 800 nm wavelength have been measured. The second harmonic coefficient is d(33) = 42.0 +/- 1.7 pm/V at the 1064 nm fundamental wavelength and is consistent with an oriented gas model. From spectroscopic ellipsometry measurements the film refractive index is 2.24 +/- 0.15 and the extinction coefficient less than or equal to 0.05 in the visible range of wavelengths. The monolayer and multilayer repeat structures were also studied by X-ray reflectivity and diffraction. The optical thickness and the oscillations in the reflectivity were in reasonable accord with a repeat length of about 3.6 nm.