Clouds are prevalent and alter PM2.5 mass and chemical composition. Cloud-affected satellite retrievals are often removed from data products, hindering estimates of tropospheric chemical composition during cloudy times. We examine surface fine particulate matter (PM2.5) chemical constituent concentrations in the Interagency Monitoring of PROtected Visual Environments network during Cloudy and Clear Sky times defined using Moderate Resolution Imaging Spectroradiometer (MODIS) cloud flags from 2010-2014 with a focus on differences in particle hygroscopicity and aerosol liquid water (ALW). Cloudy and Clear Sky periods exhibit significant differences in PM2.5 and chemical composition that vary regionally and seasonally. In the eastern US, relative humidity alone cannot explain differences in ALW, suggesting emissions and in situ chemistry exert determining impacts. An implicit clear sky bias may hinder efforts to quantitatively to understand and improve model representation of aerosol-cloud interactions.