Tissue engineering scaffolds are 3D constructs that simulate the growth environment in vivo. The present work aims to address the question of whether thin films, i.e., flat surfaces, are a suitable model for more complex 3D structures? With this in mind a complete study of the morphology and surface chemistry of poly(D,Llactide) (PDLLA) substrates, fabricated into two different structures, is presented. The polymer structures studied include a 3D, porous, foam-like scaffold prepared by the thermally induced phase separation (TIPS) method and flat polymer thin films made by solvent casting. Based on the maximum bubble point test, a new method to assess the wettability of wet pore wall surfaces inside highly porous 3D structures was developed and tested. The maximum pore diameter determined using the maximum bubble point test for the total wetting liquids was confirmed through image analysis of scanning electron micrographs. The method allows the determination of the contact angle between the wet pore wall and a contacting liquid. The captive bubble method was employed to characterise the wettability of flat polymer films in contact with water. Both structures were further characterised using zeta-(ζ-) potential measurements to assess the surface chemistry of the polymer. The results demonstrate that PDLLA contains acidic functional groups and is hydrophobic. In order to evaluate the sensitivity of the test methods, the polymer surfaces were modified by protein adsorption using fibronectin and collagen. ζ-Potential and wettability measurements show that proteins indeed adsorb on virgin PDLLA surfaces. Protein adsorption causes the wettability of the PDLLA for water to improve. Our results strongly indicate that flat surfaces are not a suitable model for surfaces in complex 3D structures such as highly porous tissue engineering scaffolds. Such scaffolds must be characterised as a 3D system.