The optimization of off-null ellipsometry is described with emphasis on the improvement of sample thickness sensitivity. Optimal conditions are dependent on azimuth angle settings of the polarizer, compensator, and analyzer in a polarizer-compensator-sample-analyzer ellipsometer arrangement. Numerical simulation utilized offers an approach to present the dependence of the sensitivity on the azimuth angle settings, from which optimal settings corresponding to the best sensitivity are derived. For a series of samples of SiO2 layer (thickness in the range of 1.8-6.5 nm) on silicon substrate, the theory analysis proves that sensitivity at the optimal settings is increased 20 times compared to that at null settings used in most works, and the relationship between intensity and thickness is simplified as a linear type instead of the original nonlinear type, with the relative error reduced to similar to 1/100 at the optimal settings. Furthermore the discussion has been extended toward other factors affecting the sensitivity of the practical system, such as the linear dynamic range of the detector, the signal-to-noise ratio and the intensity from the light source, etc. Experimental results from the investigation Of SiO2 layer on silicon substrate are chosen to verify the optimization.