The　＇Internet-of-Things＇-based　information　society　requires　the　devices　to　possess　high　scaling　capability　as　well　as　rich　functionalities.　Hybrid　systems　coupling　2D　semiconductors　and　functional　ferroelectrics　are　attracting　increasing　attention　as　complementary　devices　to　the　existing　silicon　systems　due　to　their　outstanding　electronic　and　optoelectronic　performances.　In　this　work,　interfacial　states　are　introduced　on　the　ferroelectric　Hf0.5Zr0.5O2　thin　film　during　the　annealing　process.　Utilizing　the　synergetic　effect　of　ferroelectric　polarization　and　charge　trapping　behavior,　a　multifunctional　2D　Fe-FET　is　demonstrated,　exhibiting　reliable　memory　properties,　tunable　synaptic　functions,　and　reconfigurable　photodetection　behaviors　in　one　single　device.　Among　them,　multiple　storage　levels　are　achieved　with　a　long　retention　time.　Flexible　plasticity　including　short-term　plasticity　(STP)/long-term　plasticity　(LTP)　is　emulated　successfully,　and　the　excellent　emulated　synaptic　behaviors　also　contribute　to　the　pattern　recognition　accuracy　of　≈81%　in　artificial　neural　network　simulations.　Furthermore,　the　ferroelectric　polarization-dependent　optoelectronic　response　is　observed,　making　it　promising　for　the　optoelectronic　logic　device　application.　The　results　pave　the　way　for　the　fabrication　of　high-density　data　process　systems　with　various　functions.　©　2022　Wiley-VCH　GmbH.