Solution blow spinning (SBS), is used to prepare biocompatible fibrous materials based on poly-ε-caprolactone (PCL), modified with collagen. Materials with different compositions in terms of collagen are prepared. Structure, morphology, topography, wettability behavior, and cytotoxicity are studied in order to investigate the potentiality of these materials for medical applications in the field of tissue repairing and regeneration. Structure is studied by Fourier transformed infrared spectroscopy, morphology by scanning electron microscopy, topography by optical profilometry and wettability behavior by contact angle measurements. The addition of small amounts of collagen to PCL by SBS can induce important variations in the morphology and topography of the materials that, in turns, lead to changes in the wettability behavior and ability of HaCat cells adhesion and proliferation. The analysis of surface characteristics together with the use of a model based on mats constituted by cylinders disposed perpendicularly to each other point out that, under the compositions considered, the main factor leading to higher adhesion and proliferation of cells on the PCL/collagen is the presence of more available surface area.