The adequacy of biomaterials is essential to generate scaffolds suitable for tissue engineering studies. The electrospinning technique is a resourceful, quick and cheap way to obtain polycaprolactone (PCL) scaffolds with an architecture with porosity and adequate properties to ensure the survival of cells. However, some obstacles need to be overcome, such as the hydrophilicity of this polymer. In this study, we produced electrospun PCL nanofibrous mats and submitted them to aminolysis with three different diamines in order to generate hydrophilic cell-friendly scaffolds. The nanofibrous mats were characterized by their morphology, thermal and mechanical properties and, lastly, seeded with Human Adipose-Derived Stem Cells (hADSC) to observe the influence of the introduced amino groups in the polymeric matrix. The obtained results suggest a successful insertion of amino groups in the polymeric matrix, without being too detrimental to its morphology and intrinsic properties. Furthermore, the aminolyzed mats displayed a qualitative increase of cells attached to the nanofibrous mats.