As　one　of　classic　organic　compounds,　pentaerythritol　(PE)　has　been　reported　to　have　two　phase-change　processes　with　one　solid-solid　transition　and　other　solid-liquid　transition.　To　utilize　these　two　phase-change　enthalpies　and　avoid　the　liquid　leakage　over　heat　storage　process,　this　work　for　the　first　time　proposes　to　encapsulate　PE　with　use　of　silicon　dioxide　(SiO2)　as　a　shell　substance　through　a　so-called　so-gel　technology.　The　microstructure　characterization　and　thermoproperties　as　well　as　the　cycling　performance　of　the　PE-　SiO2　composite　are　detailedly　investigated.　The　results　showed　that　PE　could　be　successfully　covered　by　SiO2　to　form　a　spherical　core-shell　structure.　Such　an　encapsulation　has　a　mean　size　of　0.3　mu　m　and　an　encapsulated　rate　of　over　77.8　%.　Due　to　the　involvement　of　two　phase-transition　stages,　the　latent　heat　of　the　PE-　SiO2　composite　reached　to　255　kJ/kg,　which　is　higher　than　other　organic　microencapsulations.　In　addition,　the　thermal　conductivity　is　largely　enhanced　by　adjusting　the　ratio　of　SiO2.　For　a　given　SiO2　ratio　of　77.8　%,　the　thermal　conductivity　of　PE-SiO2　composite　is　0.93　W/mK,　36.8　%　higher　than　that　of　pristine　PE.　Apart　from　these,　the　results　also　indicated　that　the　composite　achieves　excellent　thermal　cycling　performance.　After　one　hundred　repeated　heating-cooling　cycles,　the　latent　heat　of　the　PE-　SiO2　composite　decreases　by　less　than　5　%,　demonstrating　that　this　composite　material　has　a　large　potential　for　application　in　the　field　of　thermal　energy　storage　at　low　and　medium　temperatures.