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An aqueous extract of <i>Syzygium cumini</i> seeds was utilized to green synthesize titanium dioxide nanoparticles (TiO₂ NPs). UV-Visible, DLS, FTIR, XRD, FESEM, TEM, SAED, EDAX, and photoluminescence spectroscopy techniques were employed to characterize the prepared TiO₂ nanoparticles. The rutile crystal structure of TiO₂ NPs was revealed by XRD study. The TEM and FESEM images of the TiO₂ NPs revealed an average particle size of 50–100 nm. We employed EDAX to investigate the elemental compositions of TiO₂ NPs. The O-Ti-O stretching bands appeared in the FTIR spectrum of TiO₂ NPs at wavenumbers of 495 cm⁻¹. The absorption edge peaks of TiO₂ NPs were found in the UV-vis spectra at 397 nm. The MTT study revealed that TiO₂ NPs effectively inhibited the growth of liver cancer Hep3 and Hep-G2 cells. The results of the corresponding fluorescent staining assays showed that TiO₂ NPs significantly increased ROS generation, decreased MMP, and induced apoptosis in both liver cancer Hep3 and Hep-G2 cells. TiO₂ nanoparticles lessened SOD, CAT, and GSH levels while augmenting MDA contents in Hep3 and Hep-G2 cells. In both Hep3 and Hep-G2 cells treated with TiO₂ NPs, the Bax, CytC, p53, caspase-3, -8, and -9 expressions were remarkably augmented, while Bcl-2 expression was reduced. Overall, these findings revealed that formulated TiO₂ NPs treatment considerably inhibited growth and triggered apoptosis in Hep3 and HepG2 cells.