A casting technique was used to prepare new nanocomposite thin films of pure and GdCl 3 -or HoCl 3 -doped polyvinylpyrrolidone (PVP). Transmission electron microscopy (TEM) was used to study the particle size and dispersibility in the investigated nanocomposites. Magnetic measurements, using a vibrating sample magnetometer (VSM), were carried out at room temperature and applied magnetic fields up to 10 kO e . The appearance of hysteresis loops with small values of saturation flux density (B s ), remanent flux density (B r ), squareness ratio (SQR) and coercive field (H c ), along with permeability (l) values relatively higher than 1, may be taken, as a matter of experimentation, to consider the investigated composites as soft magnet materials. In this study, PVP-HoCl 3 films showed slightly better magnetic properties compared with PVP-GdCl 3 films. A comparative analysis of infrared (IR) and ultraviolet-visible spectra of the parent components and their composites indicated the effective role of dopant nature and concentration in morphological and microstructural changes occurring in the PVP matrix. Optical constants, such as the energy gap (E g ) and the Urbach tail (E e ), were determined and discussed in terms of a model based on the electronic transition between localized states in the band structure.