LiFeBO3/lithium boron oxide (LBO) composites with single monoclinic phase (C2/c space group) were synthesized by sol-gel method. Structure and morphology of the samples were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The electrochemical characteristics of samples were evaluated by means of the constant current charge-discharge, cyclic voltammetry (CV) and alternating current (AC) impedance. It is demonstrated that composites with LBO show higher discharge specific capacities and better cycling performance than bare LiFeBO3, especially the sample with 15.1% LBO, which delivers an initial discharge specific capacity of 194.6 mAh/g and a discharge specific capacity of 137.0 mAh/g at the 100th cycle with a rate of C/20, respectively. The observation of CV and AC impedance also indicates that the composite with 15.1% LBO evidently increases the conductivity between LiFeBO3 particles.