Micro-Raman spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy (TEM), oxygen vacancies, synchrotron X-ray absorption spectroscopy, magnetizations, optical band gaps, and photovoltaic (PV) effects have been studied in (Bi1-xLax)FeO3 (BFO100xL) ceramics for x = 0.0, 0.05, 0.10, and 0.15. XRD, Raman spectra, and TEM confirm a rhombohedral R3c symmetry with the tilted FeO6 oxygen octahedra in all compounds. The low-frequency Raman vibrations become broader and shift toward higher frequency as La3+ increases. Fe K-edge synchrotron X-ray absorptions reveal that Fe3+ valence and Fe-O-Fe bond angle are not modified by the La3+ substitution. All compounds exhibit a linear antiferromagnetic feature. Optical transmission reveals band gaps in the range of 2.22-2.24 eV. The heterostructures of indium tin oxide (ITO) film/(Bi1-xLax)FeO3 ceramics/Au film show a p-n junction-like I-V characteristic behavior. The maximal PV power conversion efficiency can reach 0.19% in ITO/BFO15L/Au under illumination of = 405 nm. A junction-like theoretical model can reasonably describe open-circuit voltage and short-circuit current as a function of illumination intensity.