Despite poly(vinyl alcohol) (PVA) hydrogel-based drug delivery systems have been extensively studied in the last years, so far there is no research investigating hydrogels in microspherical shape. In the present study, hydrogels for drug delivery systems were obtained from different formulations of poly(vinyl alcohol), poly(acrylic acid), ciprofloxacin and hydroxyapatite (Hap) aqueous solutions and shaped into spheres through dripping the solution into liquid nitrogen at extremely low temperatures. Hydrogels were then strengthened by freeze-thaw cycles. Characterisation of the samples produced aimed to evaluate the thermal (DSC), chemical (EDS), morphology (SEM), drug release properties of the hydrogel and to investigate the influence of each compound on PVA and their biocompatibility. Samples were able to maintain a spherical shape after the freeze-thawing cycles, also, cross-section of these samples revealed different internal structures depending on the components incorporated into the PVA, EDS revealed quantities of Ca and P into these hydrogels due to the HAp and the incorporation of drug, poly(acrylic acid) and hydroxyapatite increased both the melting point and the glass transition temperature of PVA. Ciprofloxacin release exhibited a burst release for approximately two hours, then stabilising the drug release to a maximum of 96.82%. PAA has acted as a release retardant and the burst release was significantly delayed. PAA chains helped encapsulating the drug and reinforced the three-dimensional structure of the hydrogel, hampering ciprofloxacin to be delivered, the total of drug release was 92.11%. Cells mortality rate (MTT) shows that PVA substrates is non-toxic for NRK cells after 24 hours of exposure.