A simple low cost, two step synthesis route, based on hydrothermal and wet chemical synthesis techniques, has been successfully adopted to prepare pure and Ni2+ doped potassium niobate-sodium niobate (KNi x Nb1-x O3-NaNbO3, x = 0, 0.02, 0.1, 0.25, 0.50) composites (by equal weight percentage). The synthesized materials have been thoroughly analyzed through XRD, FTIR, and HRTEM techniques. Further, morphological analyses through FESEM have revealed existence of mixed morphology, comprising of rod-shaped and irregular spherical structures, in the system. Diffuse Reflectance (DR) UV-Vis spectroscopy has been used to analyze the band gap values of the synthesized materials, and it has been observed that Ni2+ doping has significantly reduced the band gap values of the composites. Methylene Blue (MB) photodegradation analyses under UV irradiation have revealed absence of significant variation in the photodegradation efficiency values of the materials (photocatalysts) on doping. Dielectric studies have revealed low dielectric constant (ɛr) and loss tangent (tan δ) values, indicating an alteration to the perovskite structure of the composite materials, which in effect leads to a possible intensification of the cento-symmetric nature of the individual constituent niobate materials and thus, weakens the dielectric response of the composites in the process.