This paper presentes a new method to measure high electric field (or high voltage) by using crystalline SiO2 which has very high half wave voltage. There are many difficulties in measuring high electric field using other crystals which have generally low half wave voltage.By applying Stokes parameter and Mueller matrix. We derive optical modulation equation in the sensor which is composed of a polarizer, and Mueller matrix, we derive optical modulation equation in the sensor which is composed of a polarizer, a Pokels material, and an analyzer, We theoretically analyzed electro-optic effect, and calculated the phase retardation and half wave volt age of the birefringent material. The designed optical valtage sensor has very excellent linearity up to 20KV without divided volt-age. The maximum error was measured within 3%. Before annealing of Sio2 crystal, the maximum variation of the output voltage is 7.5% with varying temperature from ulcorner20˚c to 60˚c. But, after annealing of SiO2 crystal, the output voltage variation is improved within 1%error.