The　published　literature　focuses　on　the　electrical　performance　of　thermoelectric　envelope　and　scarcely　investigates　its　impact　on　indoor　cooling　and　heating　loads,　which　cannot　comprehensively　reflect　the　energy　saving　potential　of　thermoelectric　envelope.　In　this　work,　a　solar　thermoelectric　wall　with　phase　change　material　(STEW-PCM)　is　developed　to　investigate　its　potential　for　power　generation　round-the-clock　and　its　influence　on　the　indoor　thermal　environment　in　the　subtropical　climate.　Sensitivity　analyses　have　been　conducted　to　characterize　the　matching　relationship　between　PCM　parameters　(melting　temperature,　latent　heat　and　thickness)　and　the　proposed　system.　Meanwhile,　the　energy　saving　potential　of　STEW-PCM　system　is　forecasted　in　terms　of　annual　electrical　energy,　environmental　benefit　and　cooling　load.　The　results　show　that　STEW-PCM　system　has　the　potential　of　power　generation　round-the-clock　judging　from　the　temperature　and　output　voltage.　The　annual　electrical　energy　of　STEW-PCM　system　can　reach　1740.66　kJ/(m2·year),　corresponding　to　Levelized　Cost　of　Electricity　(LCOE)　of　35.37　c$/kJ　and　CO2　saving　cost　of　6.74　$/(m2·year).　The　cooling　load　can　be　effectively　reduced　by　more　than　25%　with　STEW-PCM　system　in　the　subtropical　climate.　This　paper　will　be　helpful　to　understand　the　dynamics　characteristics　of　a　solar　thermoelectric　wall　with　PCM　for　harvesting　energy　from　environment.　©　2023　Elsevier　Ltd