A new class of bio-nanocomposites based on hybrid gelatin-perovskite hydrogels was prepared by mixing exfoliated perovskite-tetraalkylammonium species in aqueous suspensions with gelatin solutions. Colloidal nanosheets derived from the CsCa2Nb3O10 layered perovskite re-stacked in the gelatin solutions give bio-nanocomposite materials with different content in the inorganic moiety. These films can be easily processed as homogeneous self-supported films. The partial exfoliation of the pristine mixed oxide is produced from alkylammonium exchanged phases, being the tetraalkylammonium ions (tetraethylammonium, TEA+) an efficient intermediate to give the colloid phase constituted by well exfoliated materials useful to generate homogeneous films. The nanosheets are highly oriented in the bio-nanocomposite films in agreement with the XRD patterns and the FTIR dichroism. This orientation could be considered as a characteristic of this type of hybrid materials leading to new potential applications. In this way, we have observed that the assembling of perovskite to gelatin produces a greater increase of the dielectric permittivity than the dielectric loss in the studied samples.