New experimental and analysis methods for investigating the role local environment has on photoluminescence intermittency (PI) exhibited by single luminophores are presented. Quasi-single molecule (SM) microscopy provides spatial resolution of dielectric environments within poly( vinylidene fluoride) (PVDF) films, and reveals annealing's effect on the structural phase of PVDF. New analysis methods establish that the PI exhibited by nile red (NR) SMs in PVDF are consistent with photoinduced electron transfer between NR and PVDF, where transfer rates depend on local dielectric environment. These methods should prove useful for SM studies of guest-host materials where elucidating PI contribution from the host is required. (C) 2015 Elsevier B.V. All rights reserved.