<p>Clouds are prevalent and alter fine particulate matter (PM<sub>2.5</sub>) mass and chemical composition. Cloud-affected satellite retrievals are subject to higher uncertainty and are often removed from data products, hindering quantitative estimates of tropospheric chemical composition during cloudy times. We examine surface PM<sub>2.5</sub> chemical constituent concentrations in the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network in the United States 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 PM<sub>2.5</sub> mass 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 understand and improve representation of aerosol-cloud interactions, which remain dominant uncertainties in models.</p>