The improvement of scaffold performances as cell carriers in a tissue implant is still a challenge of the regenerative medicine and tissue engineering fields. A large number of scaffolding techniques is able to produce high pore interconnectivity, different porosities and pore sizes that effectively help the cell-material interactions. Anyway, since cells in contact with a scaffold firstly sense its top surface before interacting with its macro/micro-porous structure, the insertion of chemical motifs throughout the scaffold thickness, that act as binding sites for cells, could improve the cell adhesion and colonization, not only on the external scaffold surfaces, but also inside the internal regions. In this study, combinations of plasma depositions and treatments were employed to create chemical gradients inside polycaprolactone porous scaffolds, produced with the Solvent-Casting/Particulate-Leaching technique, whose micro-morphology was finely characterized with Synchrotron Radiation Micro-Computed Tomography. The graded chemical composition of these scaffolds successfully allowed the increase of cell viability respect to untreated materials.