Energy　storage　and　conversion　in　Li-ion　batteries　involve　dynamic　Li　storage　and　transport　through　a　series　of　electrochemical　metastable　states　(or　quasi-equilibrium　configuration).　Therefore,　an　investigation　of　these　metastable　states　is　helpful　to　fully　understand　the　lithium　storage　mechanism.　An　accurate　understanding　of　the　storage　mechanism　is　a　key　factor　in　the　design　and　optimization　of　the　next-generation　high-performance　batteries.　Here,　we　report　the　results　obtained　from　electron　irradiation　induced　phase　transitions　in　Li2FeSiO4　and　LiFePO4　by　electron　microscopy.　During　prolonged　irradiation,　the　crystalline　Li2FeSiO4　particles　experienced　a　transition　from　a　monocrystalline　structure　to　an　amorphous　phase,　with　a　subsequent　recrystallization　process　(monoclinic　to　orthorhombic　phase).　The　fine　structure　of　the　electron　energy　loss　(ELNES)　spectra　showed　the　electron　beam-sensitive　characteristic　of　Li2FeSiO4　that　included　the　electron　beam-induced　mass　loss　(composition　changes),　formation　of　intermediate　metastable　states　(Li2-x,FeSiO4),　structural　distortion/amorphization　and　valence　state　variation,　all　of　which　are　much　less　prominent　in　LiFePO4　under　the　same　flux　of　electron　beam.　These　findings　provide　new　insights　into　the　structural　stability　of　Li2FeSiO4　and　LiFePO4　samples　and　is　also　important　guidance　in　the　characterization　of　electrode　materials.