In this report accelerated weathering characteristics of a novel poly(phenylene ether) (PPE)-based thermoplastic elastomer (TPE), i.e. a blend of styrene-ethylene-butylenes-styrene (SEBS)/ethylene vinyl acetate (EVA) and PPE-polystyrene (PS), were studied in detail. Exterior and interior accelerated weathering protocols were followed during photooxidative weathering to simulate outdoor and indoor (behind window glass) applications, respectively. Photooxidative degradation was monitored through optical and mechanical property measurements on the injection molded TPE. The effects of titanium dioxide and carbon black at variable loadings were also studied during the photooxidation process. Attempt was made to analyze the surface mechanical properties through nanoscratch/nanoindentation measurement. Using atomic force microscopy, surface roughness and erosion of the exposed material were investigated. Changes in chemical functionalities due to photooxidative degradation were monitored using attenuated total reflection (ATR)-FTIR. Structure property correlation was established through mechanical (surface and bulk), optical, chemical, and morphological analyses.