Polarimetry, which seeks to measure the vectorial information of light modulated by objects, has facilitated bionic geolocation and navigation applications. It is a novel and promising field that provides humans with a remote sensing tool to exploit polarized skylight in a similar way to polarization-sensitive animals, and yet few in-depth reviews of the field exist. Beginning with biological inspirations, this review mainly focuses on the characterization, measurement, and analysis of vectorial information in polarimetry for bionic geolocation and navigation applications, with an emphasis on Stokes–Mueller formalism. Several recent breakthroughs and development trends are summarized in this paper, and potential prospects in conjunction with some cutting-edge techniques are also presented. The goal of this review is to offer a comprehensive overview of the exploitation of vectorial information for geolocation and navigation applications as well as to stimulate new explorations and breakthroughs in the field.