The adsorption of two reactive copolymers poly(vinylpyrrolidone/vinyl chloroformate), poly(VP/CF), and poly(vinylpyrrolidone/vinyl chloroformate modified with N-hydroxysuccinimide), poly(VP/NHS), onto silica particles (porous and nonporous) has been studied. FTIR spectroscopy was used for the study of the adsorption onto nonporous silica particles, allowing the determination of the fractions of links between the adsorbed copolymers and the surface. A preferential adsorption of the vinylpyrrolidone units over the other ones has been observed. Moreover, a mechanism of polymer-polymer association has been demonstrated in the adsorbed layers of poly(VP/NHS). The influence of the surface structure on the adsorption has been studied with porous particles generally used for chromatography. It has been shown that the adsorption was enhanced with increased pore size for poly(VP/CF) copolymers. The porosity influence on the adsorption of the poly(VP/NHS) copolymer is complicated because of the additional interaction mechanism of polymer-polymer association.