An unprecedented wildfire impacted the northern Alberta city of Fort McMurray in May 2016 causing a mandatory city wide evacuation and the loss of 2,400 homes and commercial structures. A two-hectare wildfire was discovered on May 1, grew to ~ 157,000 ha by May 5, and continued to burn an estimated ~ 590,000 ha by June 13. A comprehensive air monitoring network operated by the Wood Buffalo Environmental Association (WBEA) in and around Fort McMurray provided essential health-related real-time air quality data to firefighters during the emergency, and provided a rare opportunity to elucidate the impact of gaseous and particulate matter emissions on near-field communities and regional air pollution concentrations. The WBEA network recorded 188 fire-related exceedances of 1-hr and 24-hr Alberta Ambient Air Quality Objectives. Two air monitoring sites within Fort McMurray recorded mean/maximum 1-hr PM2.5 concentrations of 291/5229 μg m− 3 (AMS-6) and 293/3259 μg m− 3 (AMS-7) during fire impact periods. High correlations (r2 = 0.83–0.97) between biomass combustion related gases (carbon monoxide (CO), non-methane hydrocarbons (NMHC), total hydrocarbons (THC), total reduced sulfur (TRS), ammonia) and PM2.5 were observed at the sites. Filter-based 24-hr integrated PM2.5 samples collected every 6 days showed maximum concentrations of 267 μg m− 3 (AMS-6) and 394 μg m− 3 (AMS-7). Normalized excess emission ratios relative to CO were 149.87 ± 3.37 μg m− 3 ppm− 1 (PM2.5), 0.274 ± 0.002 ppm ppm− 1 (THC), 0.169 ± 0.001 ppm ppm− 1 (NMHC), 0.104 ± 0.001 ppm ppm− 1 (CH4), 0.694 ± 0.007 ppb ppm− 1 (TRS), 0.519 ± 0.040 ppb ppm− 1 (SO2), 0.412 ± 0.045 ppb ppm− 1 (NO), 1.968 ± 0.053 ppb ppm− 1 (NO2), and 2.337 ± 0.077 ppb ppm− 1 (NOX). A subset of PM2.5 filter samples was analyzed for trace elements, major ions, organic carbon, elemental carbon, and carbohydrates. Sample mass reconstruction and fire specific emission profiles are presented and discussed. Potential fire-related photometric ozone instrument positive interferences were observed and were positively correlated with NO and NMHC.