The orientation of nematic liquid crystal (NLC) can be used in biosensor. The sensing characteristics of side-polished fiber (SPF) for determination of azimuthal orientation of NLC have been investigated. The relationship between the azimuthal angle of NLC director and the optical transmission power in SPF was derived by empirical approach. Experimental results showed that the azimuthal transition of liquid crystal affected the optical transmission power in SPF. While the azimuthal angle increased from 0° to 90°, the optical transmission power increased by 28.10dB, which is similar to the variation tendency of the empirical analysis. When it changes from 0° to 30°, the azimuthal angle is linear to the change of optical transmission power. The respondence of azimuthal angle for optical sensing is averagely 0.359dB/°. Experiments indicate that SPF can be used in determination of the azimuzal transition of NLC. It would be used for a new fiber optical biosensor based on the SPF and NLC.