The use of LiNbO3 nanoparticles in nonlinear applications is attractive and promising. The particle size and morphology of LiNbO3 are the key parameters affecting their application. In this study, spherical nanoparticles of lithium niobate were synthesised by nanosecond Nd:YAG laser ablation in water. The polycrystalline, rhombohedral structure of the synthesised LiNbO3 nanoparticles with x-ray diffraction experiments was verified. The bandgap energy of colloidal LiNbO3 nanoparticles varied between 4.25 and 4.9 eV based on the laser fluence, according to the optical characteristics. The photoluminescence (PL) reveals that the emission peaks are centered at 293, 300, 305, and 309 nm for samples prepared at 1.3, 1.6, 2.0, and 2.2 J cm−2/pulse, respectively. The transmission electron microscope investigation confirmed the formation of spherical nanoparticles with an average size ranging from 18 to 34 nm. Raman studies on nanoparticles synthesised at various laser fluences are being conducted.