We describe non‐radiative energy‐transfer experiments to measure the rates of polymer interdiffusion in P(MMA‐co‐BA) latex films formed in the presence of poly(vinyl alcohol) (PVOH). PVOH had relatively little effect on the initial efficiency of energy transfer, even when the amount of PVOH was large enough to form the continuous phase. Since ΦET(0) is a measure of the interfacial area between D‐ and A‐labeled cells in the film, we conclude that under these circumstances the dispersed P(MMA‐co‐BA) copolymer is in the form of clusters with many contacts between particles containing D and A labels. These large amounts of PVOH also reduce the amount of polymer diffusion that takes place when the films are annealed. When smaller amounts of PVOH are present, the effects are measurable but much smaller. In the presence of 2 to 17 wt.‐% PVOH, the polymer diffusion rate is retarded. The magnitude of the effect increases with the amount of PVOH present, and the effect is larger at 45 °C than at 63 °C. We show that the PVOH has its largest influence at the very early stages of polymer diffusion.