Biominerals fulfill various physiological functions in living organisms, however, pathological mineralization can also occur generating mineral pathologies such as the formation of calcium oxalate (CaOx) calculi in the urinary tract. Inspired by the ability of living organisms to generate biogenic minerals using biological organic matrices, and the need to understand the mechanisms of crystallization, three-dimensional fibrillary meshes based on chitosan fibers with random and controlled topology by electrospinning were manufactured. Chitosan was selected due to its active role on in vitro crystallization and its physicochemical properties, which allows the exposure of their functional chemical groups that could selectively stabilize hydrated crystalline forms of CaOx. CaOx crystals were generated on conductive tin indium oxide (ITO) glass substrates modified with electrospun chitosan fibers by using electrocrystallization (EC) technique. The chitosan fibers and the resulting CaOx crystals were analyzed by optical microscopy (OM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques, which demonstrated that the chemical nature and topology of the three-dimensional fibers used as organic template are key factors in the control of type, morphology, and crystallographic orientation of CaOx.