Defects and disorder work as controlling parameters to alter the electronic structure of nanostructures and significantly influence their electronic, magnetic, and nonlinear optical (NLO) properties. In this study, we found that defect engineering is an effective strategy for tailoring the linear and nonlinear optical properties of Cu-doped titanium oxide (TiO2) flower-shaped nanostructures. The concentration of chemical doping of Cu in the TiO2 lattice creates intermediate defect states that impact electronic bandgap reduction and tunable defect luminescence. The estimation of the bandgap from density functional theory calculation follows the same trend of bandgap narrowing with Cu doping. The XPS study reveals that oxygen defects are responsible for bandgap narrowing and quenching of the PL intensity. A single-beam Z-scan technique with open and closed aperture configurations using ultrashort pulses centered at 532 nm excitation wavelength was used to study the NLO measurements. The open aperture reveals saturable absorption, whereas the closed aperture shows self-focusing behavior. The nonlinear absorption coefficient and refractive index extracted from NLO measurements demonstrate the linear dependence on the defect concentration and bandgap. The effects of heterogeneous dopants and lattice disorder on the nonlinear absorption behavior of these nanostructures are discussed in comparison with the figure of merit, non-linear refractive index, and absorption coefficient. The tunable NLO properties achieved by controlling such dopant-induced defects boost the scope of these nanostructures as optical limiting, optical switching, and optical photodiode applications.