This article is focusing on electrical functionalization of biomaterial’s surface to enhance its biocompatibility. It is an overview of previously unpublished results from a series of experiments concerning the effects surface electrical functionalization can have on biological systems. Saccharomyces cerevisiae cells were used for biological experiments. The hydroxyapatite (HAp) specimens were used to investigate influence of structural point defects on the surface electrical charge. Threshold photoelectron emission spectroscopy was used to measure the electron work function of HAp and biologic samples. The density functional theory and its different approximations were used for the calculation of HAp structures with defects. It was shown that the electrical charge deposition on the semiconductor or dielectric substrate can be delivered because of production of the point defects in HAp structure. The spatial arrangements of various atoms of the HAp lattice, i.e., PO4 and OH groups, oxygen vacancies, interstitial H atoms, etc., give the instruments to deposit the electrical charge on the substrate. Immobilization of the microorganisms can be achieved on the even surface of the substrate, characterized with a couple of nanometer roughness. This cells attachment can be controlled because of the surface electrical functionalization (deposition of the electrical charge). A protein layer as a shield for the accumulated surface charge was considered, and it was shown that the protein layer having a thickness below 1 µm is not crucial to shield the electrical charge deposited on the substrate surface. Moreover, the influence of surface charge on the attachment of microorganisms, when the surface roughness is excluded, and the influence of controlled surface roughness on the attachment of microorganisms, when surface charge is constant, were also considered.