Abstract The surface characterization of 2‐(dimethylamino)ethylmethacrylate (DMA) and 2‐( N ‐morpholino)ethylmethacrylate (MEMA) homopolymers and DMA–MEMA diblock copolymer was studied using inverse‐gas chromatography (IGC). The analyzed surface properties of (co)polymers were the dispersive component of the surface energy ( $\gamma_{s}^{d}$ ) and the acid–base characters of (co)polymer surfaces. The specific free energy (Δ G sp ), enthalpy (Δ H sp ), and entropy (Δ S sp ) of adsorption of polar probes on (co)polymers were calculated. The values of Δ H sp were correlated with both the donor and the modified acceptor numbers (AN) of the probes to quantify the acidic K A and the basic K D parameters of (co)polymer surfaces. The values obtained for the K A and K D parameters indicated basic characters for the surface of (co)polymers. The dispersive component values of the surface energy and the acid–base surface parameters of the DMA–MEMA diblock copolymer surface were found to be between those homopolymers as expected. Copyright © 2008 John Wiley & Sons, Ltd.