Donor-acceptor　heterostructures　have　attracted　much　interest　in　current　optoelectronic　technologies　because　they　can　control　the　charge　dynamics　in　these　applications.　To　improve　the　charge-carrier　generation　and　transport　properties,　the　donor　and　acceptor　components　in　the　heterostructures　have　a　better　interface　at　the　molecular　level　with　bicontinuous　structures.　So　far,　most　available　examples　are　obtained　by　a　self-assembly　approach　from　two　organic　semiconducting　molecules.　Considering　the　complementary　properties　of　inorganic　and　organic　semiconductors,　the　self-assembly　of　semiconductive　inorganic　and　organic　components　in　one　material　is　anticipated　to　form　abnormal　hybrid　heterostructures　with　synergetic　properties.　However,　so　far,　only　a　few　such　hybrid　heterostructures　have　been　reported,　most　of　which　involved　in　the　inorganic　components　as　electron　donors.　Herein　we　reported　that　the　combination　of　2,5-bis-(4-pyridinium)thiazolo[5,4-d]thiazole　(Py2TTz)　with　Cu2+　in　the　presence　of　acetonitrile　by　a　solvothermal　method　led　to　a　novel　bicontinuous　hybrid　heterostructure　[Cu2(Py2TTz)(CN)2]·0.5(Py2TTz)　(1)　with　semiconducting　Py2TTz　and　in　situ　synthesized　CuCN　as　the　electron　donor　and　acceptor　components.　Due　to　the　strong　coordination　combined　with　cation-π　interactions　between　the　two　semiconducting　components,　this　hybrid　exhibits　enhanced　photocatalytic　activities　towards　the　degradation　of　methylene　blue　(MB),　rhodamine　B　(RhB),　and　methyl　orange　(MO)　in　comparison　with　those　of　the　two　individual　bulk　semiconductive　Py2TTz　and　CuCN.　©　2018　The　Royal　Society　of　Chemistry.