In this study, variable-temperature grazing-incidence X-ray diffraction, transmission electron and scanning force microscopy were employed to address the semicrystalline structure and surface morphology of thin poly(p-xylylene) – silver nanocomposite films with Ag concentrations up to 12 vol.%. It was observed that the dominant crystalline modification of poly(p-xylylene) in the studied films is α-form, which is in contrast to thick poly(p-xylylene) films deposited at liquid nitrogen temperature where β-form prevails. The films exhibit planar texture that can be further enhanced on annealing. The optical properties of the films were studied by UV–vis and IR-spectroscopy. It was found that the samples display surface plasmon resonance, with the peak wavelength in the range of 435–445 nm. The peak positions undergo a redshift upon a long-term storage under ambient conditions. The IR-spectroscopy reveals the bands, which can be assigned to the vibrations of oxygen-containing groups, with intensity increasing with silver content.