Chemical partitioning to surfaces can influence human exposure by various pathways, resulting in adverse health consequences. Clothing can act as a source, a barrier, or a transient reservoir for chemicals that can affect dermal and inhalation exposure rates. A few clothing-mediated exposure studies have characterized the accumulation of a select number of semi-volatile organic compounds (SVOCs), but systematic studies on the partitioning behavior for classes of volatile organic compounds (VOCs) and SVOCs are lacking. Here, the cloth–air equilibrium partition ratios (K CA) for carbonyl, carboxylic acid, and aromatic VOC homologous series were characterized for cellulose-based cotton fabric, using timed exposures in a real indoor setting followed by online thermal desorption and nontargeted mass spectrometric analysis. The analyzed VOCs exhibit rapid equilibration within a day. Homologous series generally show linear correlations of the logarithm of K CA with carbon number and the logarithms of the VOC vapor pressure and octanol–air equilibrium partition ratio (K OA). When expressed as a volume-normalized partition ratio, log K CA_V values are in a range of 5–8, similar to the values for previously measured SVOCs which have lower volatility. When expressed as surface area-normalized adsorption constants, K CA_S values suggest that equilibration corresponds to a saturated surface coverage of adsorbed species. Aqueous solvation may occur for the most water-soluble species such as formic and acetic acids. Overall, this new experimental approach facilitates VOC partitioning studies relevant to environmental exposure.