In the present study, hyperbranched copolymers (HBCs), namely poly(methyl methacrylate) (PMMA)-co-poly(2-hydroxyethylmethacrylate) and PMMA-co-poly(2-dimethylamino ethyl methacrylate), are photochemically synthesized by self-condensing vinyl polymerization of methyl methacrylate with the corresponding inimer using Type II photoinitiators. HBCs with different functional group and branching densities are used as surface coating materials in cellular adhesion and the respective electrochemical-based studies. After the main surface characterization of the synthesized three HBCs with contact angle measurements and atomic force microscopy, HaCaT keratinocytes and human neuroglioblastoma (U-87MG) cell lines to the surfaces are conducted. The adherence of cells is proven by both fluorescence cell imaging and electrochemical methods such as cyclic voltammetry and differential pulse voltammetry. The described strategy involving hyperbranched polymers offers great potential for fabricating various new surfaces in particular on-chip-sensing applications.