A short process for the efficient utilization of transition-metal chlorides in lithium-ion batteries (LIBs) is proposed. A uniformly dispersed tri-component nanocomposite of Ni0.8Co0.1Mn0.1O1.1 microspheres with a porous structure has been prepared from the solution of transition-metal chlorides via spray pyrolysis. When evaluated as anode for LIBs, the Ni0.8Co0.1Mn0.1O1.1 nanocomposite exhibits a reversible capacity of 1180 mAh g−1 after 120 cycles. More strikingly, the nanoparticles-assembled Ni0.8Co0.1Mn0.1O1.1 precursor has its unique advantages in synthesizing well-ordered layered LiNi0.8Co0.1Mn0.1O2, owning to its excellent atomic uniformity, porous structure and Ni3+-rich surface. The as-prepared cathode material shows excellent structural stability. Discharge capacities of 173 mAh g−1 after 100 cycles at 1 C (1 C = 180 mA g-1) between 2.8 and 4.3 V are consistently obtained, corresponding to 95.6% capacity retention. These outstanding electrochemical results are obtained with minimal process optimization, indicating that spray pyrolysis is an efficient, robust synthesis technique for the production of Ni-rich layered cathode from solution of transition-metal chlorides.