Polystyrene / polymethyl methacrylate (PS-PMMA) thin films were analyzed for detecting phase separation as well as probing their electrical responses by XPS. It was also shown that electrical parameters like resistance or capacitance can also be extracted using dynamical XPS measurements. A Kratos ES300 electron spectrometer was used for XPS measurements, and a nearby filament provided low-energy electrons for charge neutralization. The results show that under a positive stress, low-energy electrons are attracted to the sample and yield less positive charge on the sample, due to partial neutralization.