Solar　energy　conversion　is　of　great　interest　in　developing　green　and　sustainable　energy.　Herein,　we　report　the　solar-to-electricity　capability　of　a　new　two　dimensional　(2D)　Cu2S-phenol　superlattice　(CP-SL)　and　carbon　nanotubes　(CNTs)　composites　for　the　first　time.　CP-SL　is　demonstrated　to　have　a　high　Seebeck　coefficient　and　a　low　thermal　conductivity　comparable　to　that　of　metal-organic　frameworks.　CP-SL　based　solar　thermoelectric　generator　(STEG)　exhibits　stable　output　voltages　for　long　time　usages　superior　to　previously　reported　STEGs.　The　device　is　made　of　p-　and　n-type　modules　that　are　composed　of　CP-SL/CNT　and　CP-SL/polyethyleneimine　(PEI)　doped　CNTs　(PEI-CNT)　composites,　respectively.　The　polarity　of　the　composites　is　dominated　by　the　CNTs　which　have　higher　carrier　concentration.　The　carrier　transport　mechanism　in　the　composites　matches　well　with　a　parallel　model,　indicating　the　CP-SL　and　CNT　interfaces　play　a　minor　role　in　carrier　transport.　The　maximum　ZT　value　of　CP-SL/CNT　is　achieved　by　an　in-situ　growth　method,　which　is　about　35　times　higher　than　that　of　the　original　CP-SL.　These　results　indicate　that　2D　CP-SL　is　a　new　material　with　tunable　thermoelectric　properties　and　polarities,　which　may　lay　a　foundation　to　realize　p-　and　n-type　properties　in　one　material　for　single-material　organic　electronic　devices　development.　©　2021　Elsevier　Ltd