Biomass burning is a known source of brown carbon aerosol in the atmosphere. We collected filter samples of biomass-burning emissions at three locations in Canada and the United States with transport times of 10 h to >3 days. We analyzed the samples with size-exclusion chromatography coupled to molecular absorbance spectroscopy to determine absorbance as a function of molecular size. The majority of absorption was due to molecules >500 Da, and these contributed an increasing fraction of absorption as the biomass-burning aerosol aged. This suggests that the smallest molecular weight fraction is more susceptible to processes that lead to reduced light absorption, while larger-molecular-weight species may represent recalcitrant brown carbon. We calculate that these large-molecular-weight species are composed of more than 20 carbons with as few as two oxygens and would be classified as extremely low volatility organic compounds (ELVOCs).