In this study, we report on evaluation of liquid crystal (LC) cells using simultaneous surface plasmon resonance (SPR) and optical waveguide spectroscopy (OWS) technique in attenuated total reflection configuration. This technique allows for in-situ monitoring of alignment property of LC molecules adjacent to the surface and the bulk in the LC cell simultaneously. An increase of the hysteresis both for near the surface and whole cell was observed in SPR/OWS kinetic properties as the number of voltage cycling increased. The LC alignment properties after applying a DC voltage were also measured to study the effect of impurity residual ions in LC cells.