A series of organic inorganic hybrid zinc phosphites with extra-large channels were synthesized and characterized by single-crystal X-ray diffraction. This is an unusual example of introducing 1,4-benzenedicarboxylate and/or biphenyl-4,4'-dicarboxylate ligands into the organically templated metal phosphite system to build extra large-channel zeolite-related materials via hydro (solvo)-thermal reactions. Those frameworks are composed of carboxylate linkers and inorganic tubes of zinc phosphites, translating their channel windows from a square shape (NTOU-1) to rhombus forms (NTOU-2 and NTOU-3) via the replacement of organic amines or ligands under synthesis conditions otherwise identical with those used to prepare NTOU-1. The synthesis, structural diversity, photoluminescence, and adsorption properties for dye molecules and lanthanide ions are also reported.