Separators are a vital component to ensure the safety of lithium-ion batteries. However, the commercial separators employed in lithium ion batteries are inefficient due to their low porosity. In the present study, a simple electrospinning technique is adopted to prepare highly porous polyacrylonitrile (PAN)-based membranes with a higher concentration of lithium aluminum titanium phosphate (LATP) ceramic particles, as a viable alternative to the commercialized separators used in lithium ion batteries. The effect of the LATP particles on the morphology of the porous membranes is demonstrated through Field emission scattering electron microscopy. X-ray diffraction and Fourier transform infrared spectra studies suitably demonstrate the mixing of PAN and LATP particles in the polymer matrix. PAN with 30 wt% LATP (P-L30) exhibits an enhanced porosity of 90% and is more thermally stable, with the highest electrolyte uptake among all the prepared membranes. Due to better electrolyte uptake, the P-L30 membrane demonstrates an improved ionic conductivity of 1.7 mS/cm. A coin cell prepared with a P-L30 membrane and a LiFePO4 cathode demonstrates the highest discharge capacity of 158 mAh/g at 0.5C rate. The coin cell with the P-L30 membrane also displays good cycling stability by retaining 87% of the initial discharge capacity after 200 cycles of charging and discharging at 0.5C rate.