The polar bear (Ursus maritimus), with its wide-ranging movements, solitary existence and seasonal reproduction, is expected to favor chemosignaling over other communication modalities. However, the topography of its Arctic sea ice habitat is generally lacking in stationary vertical substrates routinely used for targeted scent marking in other bears. These environmental constraints may have shaped a marking strategy, unique to polar bears, for widely dispersed continuous dissemination of scent via foot pads. To investigate the role of chemical communication, pedal scents were collected from free-ranging polar bears of different sex and reproductive classes captured on spring sea ice in the Beaufort and Chukchi seas, and presented in a controlled fashion to 26 bears in zoos. Results from behavioral bioassays indicated that bears, especially females, were more likely to approach conspecific scent during the spring than the fall. Male flehmen behavior, indicative of chemosignal delivery to the vomeronasal organ, differentiated scent donor by sex and reproductive condition. Histologic examination of pedal skin collected from two females indicated prominent and profuse apocrine glands in association with large compound hair follicles, suggesting that they may produce scents that function as chemosignals. These results suggest that pedal scent, regardless of origin, conveys information to conspecifics that may facilitate social and reproductive behavior, and that chemical communication in this species has been adaptively shaped by environmental constraints of its habitat. However, continuously distributed scent signals necessary for breeding behavior may prove less effective if current and future environmental conditions cause disruption of scent trails due to increased fracturing of sea ice.