Polymeric　carbon　nitride　(PCN)　is　usually　synthesized　from　nitrogen-rich　monomers　such　as　cyanamide,　melamine,　and　urea,　but　is　rather　disordered　in　many　cases.　Now,　a　new　allotrope　of　carbon　nitride　with　internal　heterostructures　was　obtained　by　co-condensation　of　very　electron　poor　monomers　(for　example,　5-amino-tetrazole　and　nucleobases)　in　the　presence　of　mild　molten　salts　(for　example,　NaCl/KCl)　to　mediate　the　polymerization　kinetics　and　thus　modulate　the　local　structure,　charge　carrier　properties,　and　most　importantly　the　HOMO　and　LUMO　levels.　Results　reveal　that　the　as-prepared　NaK-PHI-A　material　shows　excellent　photo-redox　activities　because　of　a　nanometric　hetero-structure　which　enhances　visible　light　absorption　and　promotes　charge　separation　in　the　different　domains.　©　2019　The　Authors.　Published　by　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA.