This paper presents the electrochemical performance and characterization of nano Si electrodes coated with titanicone (TiGL) as an anode for Li-ion batteries. Atomic Layer Deposition (ALD) of the metal combined with the Molecular Layer Deposition (MLD) of the organic precursor is used to prepare coated electrodes at different temperatures with improved performance compared to the uncoated Si electrode. Coated electrodes prepared at 150° C delivers the highest capacity and best current response of 1800-1 mAhg-1 at 0.1 C and 150 mAhg-1 at 20 C. This represented a substantial improvement compared to the Si baseline which delivers a capacity of 1100 mAhg-1 at 0.1C but fails to deliver capacity at 20C. Moreover, the optimized coated electrode shows an outstanding capacity of 1200-1 at 1C for 350 cycles with a capacity decay of 93%. The improved discharge capacity, electrode efficiencies, rate capability and electrochemical stability for the Si-based electrode presented in this manuscript are directly correlated to the optimized TiGL coating layer deposited by the ALD/MLD processes, which enhances lithium kinetics as demonstrated by equivalent circuit analysis and low frequency data fitting. The coating strategy also stabilizes SEI film formation with better Coulombic efficiencies and improves long cycling stability by reducing capacity lost.