This paper presents the results of a systematic investigation of structure and formation of the interface between gold and trimethylcyclohexane polycarbonate, particularly concerning interface evolvement during gold evaporation and the influence of evaporation rate, substrate temperature, and subsequent annealing. The means of investigation were cross-sectional transmission electron microscopy, atomic force microscopy, and x-ray photoelectron spectroscopy. Extensive metal diffusion into the polymer and cluster formation near the interface were observed at deposition rates of the order of one monolayer per minute and below. The penetration depth is strongly temperature dependent. At high evaporation rates metal aggregation at the surface prevents cluster formation inside the polymer. No diffusion into the polymer was observed from metal films deposited at room temperature after extensive annealing at elevated temperatures.