Novel birefringent liquid crystal polymer homeotropic films have been coated on semiconductor solar cells to improve the effective incident sunlight angles. The liquid crystal polymer precursor, based on reactive mesogens, is fluidic and flows like liquid. It would distribute uniformly on the solar cell sample surface by any traditional coating technique. The birefringence for light, due to the liquid crystal retardation properties, manipulated the optical length and the deflection of incident light, thus allowed an increase in the energy conversion efficiency. The expensive sunlight tracking systems could be avoided. The processing parameters can be tuned such as different mesogen concentrations and plate speeds of spin-coating. The results showed that the solar cell conversion efficiency was improved from 14.56% to 14.85% at an incident sunlight angle of 15°. It was further improved from 13.40% to 13.81% when the angle was 30°. The interesting angular dependency on solar cell efficiency enhancement has been evaluated.