Ni-doped LaFeO3 (LFO) microsphere consisting of nanoparticles are synthesized by the hydrothermal route and used for the degradation of Rhodamine B (RhB) organic dye. The structural, morphological, and optical analysis is confirmed by the various characterization techniques, i.e., X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and UV-Visible spectroscopy. The all Ni-doped LFO catalyst shows excellent efficiency towards the photocatalytic degradation of RhB dye. LFNO-0.2 catalyst shows the highest degradation efficiency of 89.44% with rate constant (k) and correlation coefficient (R2) of 0.013304 min-1 and 0.989, respectively. The radical scavenging suggests the active involvement of O2- and h+ participates in the efficient degradation. Moreover, the material possesses excellent cyclic stability for the continuous Xenon lamp exposure of 540 min. Overall, the Ni-doped LFO can serve as one of the finest materials for wastewater remediation by means of photocatalytic dye degradation.