This research investigates the influence of certain vitamins (A and D2) on the possibility of hydroxyapatite formation on polymer surfaces. A coating method based on biomimetic techniques was used to form a crystalline hydroxyapatite thin layer on porous polyurethane matrix. The method is based on a wet process of hydroxyapatite formation that involves porous polyurethane film soaking in a modified synthetic Simulated Body Fluid (SBF) solution. This modified SBF solution contains vitamin A and vitamin D2. The deposited hydroxyapatite layers were investigated by scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX). The results obtained in this research suggest that the formation of hydroxyapatite layer on polymeric substrate is favored by the presence of vitamins A and D2 in SBF solution. Therefore, this modified method can be used to obtain porous composites based on polyurethane and hydroxyapatite which can be used in bone tissue replacement, with pediatric and adult applications, or in separation processes.