We report the optical and magnetic properties of single-crystalline Ca and Ti co-substituted bismuth ferrite, Bi1-xCaxFe1-xTixO3, nanoparticles, synthesized by a facile sol-gel methodology in the compositional range wherein 0 <= x <= 0.25. X-ray diffraction (XRD) and transmission electron microscopy (TEM) investigations show that all samples possess a rhombohedrally distorted perovskite structure with space group R3c. Ca and Ti co-substitution controls the formation of secondary phases and improved the stability of perovskite phase of BiFeO3. The average particle size was estimated by Williamson Hall plot, confirmed by TEM, and found to be about 59, 50, 46, 41, 40 and 38 nm of Bi(1-x)Ca(x)Fe(1-x)Ti(x)O(3)for x = 0, 0.05, 0.10, 0.15, 0.20 and 0.25, respectively. The UV-vis absorption study reveal the strong absorption of visible light with a small optical band gap (1.77-2.25 eV) for 0 = x = 0.25 indicates a possibility of utilizing for photocatalytic activities. The magnetic study at room-temperature displays the improved magnetization and coercive field in Bi1-xCaxFe1-xTixO3 nanoparticles due to the release of the latent magnetization locked within the toroidal spin structure of BiFeO3. (C) 2016 Elsevier B.V. All rights reserved.