The polyanion-type compounds Li2MSiO4 (M = Fe, Co and Mn) with high theoretical capacities, environmental friendliness and low-cost, have long been considered as one of the most promising cathode materials for lithium-ion batteries (LIBs). However, they are rarely reported as anode materials. Herein, Li2FeSiO4 (LFS), Li2CoSiO4 (LCS) and Li2MnSiO4 (LMS) based materials were prepared by a sol–gel method and the subsequent calcination, which were systematically investigated as anode materials for LIBs. Due to the slowest nucleation rate of the precursor during the sol–gel process, the calcination product LFS particles are the smallest. Since small particles offer more capacitive contribution and the auxiliary species Fe3O4 provides more capacity, LFS has the largest capacity of 661.4 mAh g−1 at 0.2 A g–1 after 300 cycles, which is higher than LCS and LMS. Inspired by the large capacitive contribution of LFS for LIBs, LFS is also applied for aqueous lithium-ion capacitors, which can obtain a capacitance of 78 F g−1 at 1 A g–1. This work will provide an explanatory idea for a range of substances with analogical chemical formula but different lithium storage properties.