This paper describes a study of surface derivatisation methods applied to two-dimensional polymer matrices microfabricated using the Pressure-Assisted Microsyringe (PAM) technique. A blend of polylactide and polycaprolactone was used as the matrix material, and surface chemistry techniques based on silanes and polyethyleneglycol (PEG) derivatives were employed to render the surface underlying the scaffold anti-adhesive whilst polylysine was covalently coupled to the surface of the polymer matrix to enhance cell adhesion. Prior to cell-adhesion tests, the surfaces and matrices were analysed using physico-chemical techniques, such as surface tension, surface potential and fluorescence. Adhesion of primary endothelial cells was evaluated using cell counting techniques. The results demonstrate that both PEGs and silanes are about 66% efficient at demarcating endothelial cell adhesion in short term experiments and that covalently-bound polylysine to the polymer matrix increases cell adhesion twofold with respect to the adsorbed polypeptide.