Optical navigation techniques were required to successfully complete the planetary exploration phase of the NASA deep-space Voyager mission. The last of Voyager's planetary encounters, with Neptune, posed unique problems from an optical navigation standpoint. In this paper we briefly review general aspects of the optical navigation process as practiced during the Voyager mission, and discuss in detail particular features of the Neptune encounter which affected optical navigation. New approaches to the centerfinding problem were developed for both stars and extended bodies, and these are described. Results of the optical navigation data analysis are presented, as well as a description of the optical orbit determination system and results of its use during encounter. Partially as a result of the optical navigation processing, results of scientific significance were obtained. These results include the discovery and orbit determination of several new satellites of Neptune and the determination of the size of Triton, Neptune's largest moon.