In this study, we employed several experimental techniques to investigate structure and magnetic properties of poly(p-xylylene)–MnSb composites synthesized by low-temperature vapor deposition polymerization technique and MnSb films deposited at various temperatures. The presence of MnSb nanocrystallites in the studied films was verified by the results of X-ray diffraction, electron microscopy and Raman spectroscopy studies. The obtained data revealed the formation of Sb-rich sublayer with well-oriented Sb grains near the susbtrate, which seems to act as a buffer for the consequent poly(p-xylylene)–MnSb or MnSb layer growth. Increasing the polymer content results in qualitative change of surface morphology of studied films. At high polymer content the hybrid nanocomposite with MnSb nanoparticles embedded into poly(p-xylylene) matrix is formed. All investigated samples demonstrated detectable ferromagnetic response at room temperature, while the parameters of this response revealed a complex correlation with nominal composition, presented crystal phases and surface morphology of studied films. Estimated values of the Curie temperature of the samples are close to that of bulk MnSb.