This study discusses the nonlinear optical properties of as-grown and annealed NiO thin films using the Z-scan technique utilizing the femtosecond laser pulses at a repetition rate of 100 kHz of wavelength 1030 nm with a pulse duration of 370 fs. In open aperture measurements, pristine reveal saturable absorption (SA) with a negative sign of nonlinearity, while annealed samples exhibit reverse saturable absorption (RSA) with a positive sign of nonlinearity. In closed aperture conditions, all samples show prefocal minima and postfocal maxima, indicating self-focusing behavior. The observed RSA phenomena are attributed to the indirect two-photon absorption (TPA) process. The influence of surface plasmon resonance on nonlinear absorption is successfully ruled out due to insufficient excitation energy (1.20 eV) to induce resonance in the samples. The increase in bandgap with annealing temperature, associated with indirect TPA, is elucidated with the shifting of Ni-dx2-y2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$d_{x^2-y^2}$$\\end{document} and Ni-dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$d_{z^2}$$\\end{document} orbitals in the conduction band, under the framework of Density Functional Theory (DFT). The DFT results are correlated with the observed nonlinear SA and RSA processes. The Ni d-d and Ni-d to O-p transitions contribute to the modulation of nonlinearity in the indirect TPA process. The study suggests that the sample annealed at 400 °C exhibits superior optical limiting properties with the highest nonlinear absorption coefficients compared to the other annealed sample, while the as-grown sample is suitable for passive Q-switching applications.