Carbonaceous materials are the dominant anode materials for lithium-ion batteries since their launch by Sony in 1991. Despite the significantly higher energy density found in silicon, unstable interface and volumetric changes during lithiation and delithiation have prevented the move to silicon-based anodes. Materials and morphological design have been focused to mitigate the structural instabilities that arise during lithium insertion and removal. This paper will introduce a different approach, surface modification, that have been developed recently to accommodate volume expansion and contract, but also modify the surface of silicon against electrical isolation following pulverization, and improve the electronic and ionic conductivities of silicon anodes during operation and cycling. Besides wet chemistry, atomic layer deposition (ALD) and molecular layer deposition (MLD) methods have been utilized to produce polymeric hybrid inorganic-organic coating covalently bonded to surface of silicon particles. Improved performance, including high rate capability and durable cycling, has been achieved for the ALD/MLD coated electrodes. To further investigate the impact of surface modification on the electrochemical behavior, in-situ characterization and molecular simulation have been used to study the morphological evolution and surface structure during electrochemical reactions. The data from the synthesis and analysis shed light on the importance of surface modification for silicon-based electrodes. The results provide the information for new design of surface coatings for electrode materials with the aims of achieving durable high-energy-density lithium-ion batteries.