In this article we use fluorescence resonance energy transfer (FRET) to investigate how a classic coalescing aid, such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol (TM)) (TX), acts on the earliest stages of polymer diffusion as the latex film is still drying. In our approach, we temporarily arrest the drying process of a partially wet latex film by sealing it in an airtight chamber previously cooled to near the latex T-g. At these conditions, we are able to effectively stop the drying process and the polymer diffusion. FRET measurements at various locations on such a sample provide us information about the mechanism operating at the initial stages of polymer diffusion as the latex film is still drying. We complete our study with FRET measurements carried out at longer aging times on predried latex films. We analyze our diffusion data in terms of free volume theory and propose a mechanism that can account for the results obtained. (C) 2011 Elsevier Ltd. All rights reserved.