An evolutionary modification approach, boron doped carbon coating, is initially used to improve the electrochemical properties of electrode materials of lithium‐ion batteries, such as Li 3 V 2 (PO 4 ) 3 , and demonstrates apparent and significant modification effects. Based on the precise analysis of X‐ray photoemission spectroscopy results, Raman spectra, and electrochemical impedance spectroscopy results for various B‐doped carbon coated Li 3 V 2 (PO 4 ) 3 samples, it is found that, among various B‐doping types (B 4 C, BC 3 , BC 2 O and BCO 2 ), the graphite‐like BC 3 dopant species plays a huge role on improving the electronic conductivity and electrochemical activity of the carbon coated layer on Li 3 V 2 (PO 4 ) 3 surface. As a result, when compared with the bare carbon coated Li 3 V 2 (PO 4 ) 3 , the electrochemical performances of the B‐doped carbon coated Li 3 V 2 (PO 4 ) 3 electrode with a moderate doping amount are greatly improved. For example, when cycled under 1 C and 20 C in the potential range of 3.0–4.3 V, this sample shows an initial capacity of 122.5 and 118.4 mAh g −1 , respectively; after 200 cycles, nearly 100% of the initial capacity is retained. Moreover, the modification effects of B‐doped carbon coating approach are further validated on Li 4 Ti 5 O 12 anode material.