Per- and polyfluoroalkyl substances (PFAS) and pesticides are globally distributed contaminants that persist in terrestrial food webs, yet baseline data for large omnivores in the continental U.S. remain limited. This study quantified PFAS and pesticides in whole blood from free-ranging black bears (Ursus americanus, n = 15) and grizzly bears (Ursus arctos horribilis, n = 9) in the Cabinet-Yaak Ecosystem of northwestern Montana. Using high-resolution mass spectrometry-based methods (GC-MS/MS and LC-MS/MS), 52 PFAS and 186 pesticides were analyzed. PFAS were detected in all bears, with total PFAS concentrations ranging from 79.5 to 317 pg/mL. PFAS profiles were dominated by long-chain perfluoroalkyl carboxylic acids, particularly PFOA, PFDA, and PFUnDA, with minimal contribution from short-chain compounds. Species was the strongest ecological predictor of PFAS concentrations, although variability across age, sex, and capture location were observed. Only two pesticides, piperonyl butoxide and permethrin, were detected at quantifiable concentrations (2070–12,600 pg/mL), and no correlations were observed between pesticide and PFAS concentrations, indicating independent exposure pathways. The predominance of long-chain PFAS suggests diffuse environmental sources and bioaccumulation within terrestrial food webs. Although measured concentrations were generally low relative to other wildlife toxicological studies, the persistence and protein-binding properties of long-chain PFAS warrant continued monitoring, particularly for long-lived omnivores. These results establish baseline contaminant concentrations for two apex omnivores in a remote ecosystem and highlight the utility of large mammals as integrative sentinels of environmental contaminant exposure for regional monitoring and wildlife conservation. Continued monitoring in the Cabinet-Yaak and across western North America will be critical for assessing temporal trends, identifying new contaminant sources, and evaluating ecological health in bear populations.