Hair care cosmetics are used for cleaning, damage prevention from external agents and making hair healthier. The use of film‐forming polymers in these formulations ensures the correction of hair cuticle imperfections and the reduction of water loss, making hair softer and thicker. For this reason, in the present work, N‐vinyl‐2‐pyrrolidone homopolymers and copolymers with acrylic acid, methacrylic acid and vinyl acetate are produced through aqueous solution polymerizations, investigating some properties of the final products and respective polymer films for use in capillary cosmetic applications. The obtained results show that the poly(N‐vinyl‐2‐pyrrolidone) (PVP) homopolymer and copolymer samples can be obtained with high molar masses, providing films that can interact appropriately with keratin. Besides that, it is shown that acrylic acid and methacrylic acid can be successfully incorporated into the PVP chains during the copolymerization reactions, resulting in the improvement of the mechanical properties of the film, but affecting negatively the polymer‐keratin interaction.