There has been rising concentration on the photodiode properties of the MS devices in recent years to improve the performance of light sensing devices. Therefore, in this study, LiCoO2 was synthesized via sol–gel-based electrospinning method and it is used as interlayer between Al and n-type Si to fabricate Al/LiCoO2/n-Si photodiode via ultrasonic spray pyrolysis and physical vapor deposition methods. LiCoO2 thin film was characterized via XRD, SEM and AFM. Crystallite size for LiCoO2 was found to be 37.75 nm. Electrical characterization was performed by current–voltage (I- V) and current-transient (I- t) measurements using solar simulator under dark and various illumination conditions. I- V characteristics demonstrated that the Al/LiCoO2/n-Si exhibited good photodiode behavior and a high rectifying ratio. Moreover, LiCoO2-interlayered device has shown significant responsivity and detectivity. It has shown 1.79 × 1010 Jones detectivity and 0.364 A/W responsivity at 100 mW light power. Thus, the results demonstrate that a device based on LiCoO2 can be employed in optoelectronic applications.