The combination of precision-controlled weight loss measurements and spectroscopic surface FT-IR analysis allowed us to identify unique behaviors of poly(methyl methacrylate) (p-MMA). When MMA and n-butyl acrylate (nBA) are polymerized into p-MMA and p-nBA homopolymer blends, MMA/nBA random copolymers, and p-MMA/p-nBA core-shell morphologies, a controlled mobility and stratification of low molecular weight components occurs in films formed from coalesced colloidal dispersions. Due to different affinities toward water, p-MMA and p-nBA are capable of releasing water at different rates, depending upon particle morphological features of initial dispersions. As coalescence progresses, water molecules are released from the high free volume p-nBA particles, whereas p-MMA retains water molecules for the longest time due to its hydrophilic nature. As a result, water losses at extended coalescence times are relatively small for p-MMA. MMA/nBA copolymer and p-MMA/p-nBA blends follow the same trends, although the magnitudes of changes are not as pronounced. The p-MMA/p-nBA core-shell behavior resembles that of p-nBA homopolymer, which is attributed to significantly lower content of the p-MMA component in particles. Annealing of coalesced colloidal films at elevated temperatures causes migration of SDOSS to the F-A interface, but for films containing primarily p-nBA, reverse diffusion back into the bulk is observed. These studies illustrate that the combination of different particle morphologies and temperatures leads to controllable permeation processes through polymeric films.