A humidity control system was operated upstream of two collocated MOUDIs (micro-orifice uniform deposit impactors) for sampling ambient aerosol particles. One MOUDI used silicone-grease-coated aluminum foils (ALs) as the impaction substrates and was considered as the reference impactor, while the other used uncoated ALs or uncoated Teflon filters (TFs) as the impaction substrates for quantifying the effect of different relative humidities (RHs) and impaction substrates on the PM0.1 concentrations and mass distributions of ambient PMs. Test results showed that decreasing RH in general increased particle bounce from uncoated substrates with the bounce from uncoated ALs being more severe than that from uncoated TFs. Particle bounce did not influence the overall mass distribution of ambient fine particles when RH ranged between 40% and 80%, whereas it led to undersampling of particles greater than 2.5 μm in aerodynamic diameter severely. Oversampling of PM0.1 occurred by as much as 95%-180% or 25%-55% when the MOUDI used uncoated ALs or TFs, respectively, as RH was reduced from 50% to 25%. Particle bounce was found to be negligible, and PM0.1 and PM2.5 could be sampled accurately with less than 5% error at the RH of 75%-80% or 65%-80% when uncoated ALs or TFs were used, respectively.