Owing to the confinement of ZnO in the photocatalytic application: the wide bandgap, the rapid photogenerated carriers recombination, and the expensive cost for the catalyst separation from the wastewater, the p-n heterojunction of NiFe2O4 magnetic phase and ZnO is considered to improve the photocatalytic efficiency and the catalyst separation by the external magnetic. The NiFe2O4/ZnO composites with 0-12 wt% of NiFe2O4 were prepared by an ordinary process and characterized using XRD, Raman, SEM, EDS, TEM, HRTEM, UV-Vis spectroscopy, and PL techniques. The Raman spectra confirm the crystallinity of ZnO and NiFe2O4, including their defects. As increasing NiFe2O4 incorporation, the crystallite size of ZnO phase depicts a lower value with changing from 53.14 to 40.49 nm, whereas NiFe2O4 phase reveals a greater value of 60.61-141.55 nm. The dislocation density, lattice constants, and atomic coordinates are also discussed in terms of ion diffusion. The morphology analysis reveals ZnO particles on the surface of NiFe2O4 microcrystals, confirming the p-n heterojunction formation. The energy bandgap of the as-synthesized samples is in the range of 1.52-2.85 eV, suggesting to the visible light photocatalysis. The prominent PL spectrum indices the forming of Zn interstitial defect state. Under the visible light irradiation, the dye degradation was investigated as a result of the photoreduction percentage and catalyst dosage. With prepared by a facile process, 12 wt% NiFe2O4-loaded ZnO displayed the high methylene blue degradation of 96.96 % within 150 min under visible light irradiation, confirming an excellent photocatalyst. Due to the microstructural composite, the active surface site and the p-n heterojunction were elucidated as the principal mechanism for the difference in reaction time. The dye degradation was discussed in association with the structural constants, morphology, and defects.