Titanium diselenide (TiSe2) is the least studied member of the transition metal dichalcogenide family due to a lack of available synthesis methodology, controlled bandgap engineering, and rapid characterization of layers. In this paper, we report the chemical exfoliation of TiSe2 platelets synthesized by the chemical vapor transport route in ortho-dichlorobenzene (o-DCB) functionalized with oleylamine (OLA), for the first time to the best of our knowledge. It is found that the addition of OLA supports the formation of a stable dispersion of a large area of the TiSe2 sheets due to surface capping with the OLA molecules indicating the importance of the ligand in dispersion behavior. The X-ray diffraction pattern confirms the hexagonal structure of the TiSe2 platelets with the space group P3[combining macron]m1 while Raman spectroscopy reveals that two modes of vibration i.e. A1g and E2g exist with layered structures having dimensions in micrometers as confirmed by scanning electron microscopy. Fourier transform infrared spectroscopy confirms the successful functionalization of chemically exfoliated TiSe2 nanosheets. Field-emission scanning electron microscopy reveals that exfoliated TiSe2 has a thickness of 15-55 nm whereas high-resolution transmission electron microscopy indicates thicker sheets for ligand-free exfoliated TiSe2 which are crystalline. Atomic force microscopy confirms the formation of nanosheets. UV-Visible, photoluminescence, and time-resolved PL spectroscopy showed an enhanced effect and better average lifetime of excitation for the exfoliated sheets with OLA than those without OLA. The C-V studies reveal that with increasing scan rate, the corresponding current also increases. The present study offers the possibility of their utilization in optoelectronics, advanced low-power electronics, voltage-controlled oscillators, ultra-fast electronics, and electrochemical devices.