The loss of optical transparency when polymer films are immersed in water, which is called "water whitening," severely limits their use as clear barrier coatings. It is found that this problem is particularly acute in films deposited from polymers synthesized via emulsion polymerization using surfactants. Water whitening is less severe in secondary dispersion (SD) polymers, which are made by dispersing solution polymers in water without the use of surfactants. NMR relaxometry in combination with optical transmission analysis and electron microscopy reveal that some of the water sorbed in emulsion polymer films is contained within nanosized "pockets" or bubbles that scatter light. In contrast, the water in SD polymer films is mainly confined at particle interfaces, where it scat-ters light less strongly and its molecular mobility is reduced. The addition of surfactant to a SD creates a periodic structure that displays a stop band in the optical transmission. The total amount of sorbed water is not a good indicator of polymers prone to water whitening. Instead, the particular locations of the water within the film must be considered. Both the amount of water and the size of the local water regions (as are probed by NMR relaxometry) are found to determine water whitening. (C) 2016 Wiley Periodicals, Inc.