Copolymers comprising 2-methacryloyloxyethyl phosphorylcholine (MPC) and hydrophobic methacrylic esters were used as biomembrane-mimetic polymers to provide blood compatibility. In the present study, we compared the surfaces coated with two MPC polymers with different alkyl groups, namely, poly(MPC-co-butyl methacrylate) (PMB) and poly(MPC-co-dodecyl methacrylate) (PMD), to clarify the effect of their hydrophobic units. Various substrates, such as poly(ethylene terephthalate), polycarbonate, polypropylene, acrylonitrile-butadiene-styrene copolymer, and stainless steel, were coated with ethanol solutions containing various concentrations of PMD or PMB. The solubility of PMD in ethanol changed depending on the water content. Scanning probe microscopy and rhodamine 6G staining revealed heterogeneous microstructures on the PMD-coated surface but not on the PMB-coated surface. Adhesion of various cells was efficiently suppressed by the PMD coating at lower concentration than the PMB coating, except regarding the adhesion of macrophage-like RAW264.7 cells. Our results suggest that the dodecyl groups in PMD increased its affinity for the substrates and simultaneously induced the formation of hydrophobic domains recognized by RAW264.7 cells.