The adsorption of pyridine and its derivatives on the graphene surface has been studied using density functional theory (DFT). Adsorption geometries and energies as well as nature of binding have been analyzed. Dispersion effects have been taken into account via a semiempirical DFT-D2 method. Influence of electron-donor and electron-acceptor substituents in 4-position of the heterocyclic ring, effect of substrate and adsorbate’s concentration on the interaction energy have been investigated. Impact of the pyridine adsorption on the electronic band structure of graphene has been studied.