As a cathode material for lithium ion rechargeable batteries, LiNi0.8Co0.2O2 (LNCO) is one of the most attractive candidates for high power electronic devices. In the present work, we have synthesized LNCO powder by solid-state route. The discharge capacity and the capacity retention of LNCO cathode are found to be ∼100mAhg−1 and ∼63%, respectively. Molybdenum doping, replacing parts of cobalt ion in LNCO lattice increases the discharge capacity (∼157mAhg−1) and improve its capacity retention characteristics. Through X-ray Rietveld analyses, we have found that Mo doping increases the inter-slab spacing between the (Co,Ni)O2 octahedral layers which provides easier Li1+ intercalation leading to improved electrochemical properties in the modified cathode.