The reorientation behavior of nematic liquid crystal molecules induced by an electric pulsed field was investigated by means of time-resolved optical waveguide spectroscopy (TROWS) which was developed to observe transient changes in dielectric constants and to measure the thickness of a thin dielectric medium. Time evolution of the waveguide mode patterns was successfully obtained by using TROWS, which records the reflectivity as both functions of the incident angle of laser light and the time from switching-on or -off of the external electric field. The transient dielectric tensor profile in the 4′-pentyl-4-cyanobiphenyl (5CB) layer both after switching-on and -off of the electric field could be precisely determined in a three-dimensional coordinate system by using Deuling's theory which treats the orientational deformation induced by an external electric field. Theoretical analysis of TROWS data clearly indicated that half of the 5CB molecules rotate clockwise in the plane defined by the rubbing direction and the substrate normal, and the other half rotates counter-clockwise in the same plane. The counter rotation compensates the effect of birefringence observed in the direction parallel and perpendicular to the rubbing direction and the reorientation kinetics could be well described by the Ericksen-Leslie equation. Relaxation behavior from homeotropic to planar orientation could be treated as an orientation diffusion process by applying a Gaussian distribution function to the maximum tilting angle at the middle of the cell. We report the usefulness of TROWS which provided more detailed information about the dynamics of the 5CB molecules.