The　design　and　construction　of　metal　organic　frameworks　(MOFs)　or　coordination　polymers　(CPs)　with　tunable　structures　is　of　great　interest　in　recent　years,　owing　to　their　intriguing　structural　diversity　and　potential　applications.　The　mixed-ligand　approach　is　widely　used　as　an　effective　synthesis　method　to　fabricate　CPs.　By　precise　regulation　of　the　structure　of　N-donor　co-ligands,　in　this　work,　a　series　of　zinc/cadmium-organic　arsonates　are　successfully　synthesized,　namely,　[Zn2(OH)(L-As)(4,4′-Bipy)⋅H2O]n　(1),　[Zn3(L-As)2(2,2′-Bipy)(H2O)2⋅2H2O]n　(2),　[Cd(HL-As)(4,4′-Bipy)0.5]n　(3),　[Cd(HL-As)(2,2′-Bipy)(H2O)⋅H2O]n　(4)　(H3L-As　​=　​2-(carboxymethylamino)phenylarsonic　acid;　4,4′-Bipy　​=　​4,4′-bipyridine;　2,2′-Bipy　​=　​2,2′-bipyridine).　We　demonstrate　that　N-donor　co-ligands　significantly　affect　the　coordination　environment　of　metal　centers　and　the　structure　of　these　compounds.　Compound　1　is　a　three-dimension　(3D)　hydrogen-bond　network　via　C–H···π　interactions　between　the　aromatic　rings　of　L-As　ligand,　whereas　3　exhibits　a　3D　framework　with　6-connected　pcu　topological　network.　By　contrast,　2　and　4　are　two-dimension　(2D)　layered　structures　by　adopting　chelated　2,2′-Bipy　Co-ligand.　All　compounds　display　a　luminescence　from　ligand-to-metal　charge　transfer　(LMCT)　which　depends　on　the　coordination　environment　of　metal　centers.　The　results　show　that　N-donor　co-ligands　can　effectively　regulate　the　structures　and　luminescent　properties　of　the　formed　CPs.　©　2022　Elsevier　Inc.