A series of polymer and copolymer networks with varying hydrophilicity and distribution of the hydrophilic groups was synthesized and biologically tested with monolayer culture of human chondrocytes in vitro. Cell viability (MTT), proliferation (BrdU incorporation) and aggrecan expression (PG ELISA) were quantified at 7 and 14 days from seeding. Both assays (MTT and BrdU) showed complementary results that are consistent with positive cellular adhesion on the material. When human chondrocytes were cultured on polymer substrates in which the hydrophilic groups were homogeneously distributed, hydrophobic substrates showed higher values in all the biological parameters analysed. Adhesion, proliferation and viability decreased monotonously with the content of hydrophilic groups in the polymer chain. However poly(ethyl acrylate-co-hydroxyethyl methacrylate) copolymers, in which hydrophilic and hydrophobic nano-domains alternate as phase-separated domains, showed better results than the corresponding homopolymers.