Charge-discharge capacity and cyclicity of lithium ion battery (LIB) was evaluated in which 15Li2O·10Fe2O3·xSnO2·5P2O5·(70–x)V2O5 glass (x = 0 and 20 in mol%, abbreviated as xLFSPV) was used as a cathode. A local structure of xLFSPV glass before and after charging was investigated by 57Fe- and 119Sn-Mossbauer spectroscopies. 57Fe-Mossbauer spectrum of xLFSPV glass with ‘x’ of 20 was composed of a doublet with isomer shift (δ) of 0.35±0.02 mm s − 1 and quadrupole splitting (Δ) of 0.88±0.03 mm s − 1 due to distorted FeIIIO4 tetrahedra. 119Sn-Mossbauer spectrum of this glass consisted of a doublet with δ of 0.08±0.01 and Δ of 0.52±0.01 mms − 1 due to distorted SnVIO6 octahedra. After discharging the battery from 4.5 to 1.0 V, larger δ of 0.40±0.03 mm s − 1 and Δ of 0.94±0.04 mm s − 1 were obtained, indicating that both iconicity of Fe-O bonds and local distortion of FeIIIO4 tetrahedra were increased. On the contrary, identical δ of 0.09±0.01 mm s − 1 and Δ of 0.50±0.01 mm s − 1 were observed in the 119Sn-Mossbauer spectrum of 20LFSPV glass after the discharge, indicating that chemical environment of SnIVO6 octahedra was not affected after the discharge. Charge-discharge curve of LIB containing 20LFSPV glass as a cathode active material recorded under the current density of 8.3 mA g − 1 (0.011 mA cm − 2) between 1.0 and 4.5 V showed a large initial charge capacity of 431.1 mAh g − 1 and discharge capacity of 382.3 mAh g − 1, respectively. These results indicate that 20LFSPV glass could be a new cathode active material for LIB.