Pressure-induced phases of ZnO have attracted considerable attention owing to their excellent electronic and optical properties. This study provides a vital insight into the electronic structure, optical characteristics, and structural properties of the AsTi (B_i) phase of ZnO under high pressure via the DFT-based first-principles approach. The phase transformation from BN(B_k) to the B_i phase of ZnO is estimated at 16.1 GPa using local density approximation, whereas the properties are explored precisely by the hybrid functional B3LYP. The electronic structure exploration confirms that the B_i phase is an insulator with a wider direct bandgap, which expands by increasing pressure. The dielectric function evidenced that the B_i phase behaves as a dielectric in the visible region and a metallic material at 18 eV. Optical features such as the refractive index and loss function revealed the transparent nature of the B_i phase in the UV range. Moreover, the considered B_i phase is found to possess a high absorption coefficient in the ultraviolet region. This research provides strong theoretical support for the development of B_i-phase ZnO-based optoelectronic and photovoltaic devices.