The effects of vinylene carbonate (VC) as an electrolyte additive on a 3-dimensionally ordered mesoporous carbon based lithium ion battery are investigated. Our investigation reveals an optimal concentration of VC, which improves the discharge specific capacity at the 100th cycle to 844.3 from 684.3 mAh g−1, and improves the first cycle’s coulombic efficiency to 32.4 from 23.7%. The improvements are revealed to be a result of reduced charge transfer and solid electrolyte interface resistance, enabling better permeability of Li ions. This work demonstrates that VC is a viable electrolyte additive in improving the performance of a non-graphitic carbonaceous material.