Lithium-rich layered cathode materials have drawn great attention in lithium-ion cells owing to their high theoretical specific capacity and high working voltage. In this study, a lithium-rich layered cathode, Li1.5Ni0.25Mn0.75O2.5 (LNMO) is synthesized by a carbonate co-precipitation method and further coated with bio-synthesized TiO2 nanoparticles. The effect of nano-TiO2 coating on the electrochemical performance and thermal stability was thoroughly studied. The results reveal that the 2 wt% TiO2-coated sample shows excellent capacity retention (∼89.3% capacity retention at 1 C rate after 200 cycles) whereas, the pristine LNMO shows severe capacity fading (only 78.4% capacity retained after 100 cycles at 1 C) and voltage decay. The coated sample also exhibits superior rate performance than the pristine sample (181.6 mAh g−1 for 2 wt% TiO2-coated LNMO and 113.3 mAh g−1 for pristine LNMO, at 2 C). Moreover, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analyses demonstrate the enhanced thermal stability of the 2 wt% TiO2-coated sample under charged condition.