By systematically varying the geometric length and electronic properties of the second ligating ligands of halogen (Cl-, Br-, and I-) and pseudohalogen (CN-, SCN-, and N-3(-)) anions, we synthesized 11 isomeric/isostructural copper(I) complexes: [Cu-2(L3-3)I](n) (1), [Cu-2(L4-4)Br](n) (2-Br), [Cu-2(L4-4)Cl](n) (2-Cl), [Cu-2(L3-4)(CN)](n) (3), [Cuz(L3-3)(CN)](n) (4), [Cu-3(L4-4)(CN)(2)](n) (5), {[Cu-2(L4-4)-Br](2)center dot CuBr}(n) (6-Br), {[Cu-2(L4-4)Cl](2)center dot CuCl}(n) (6-Cl), [CU2(L4-4)-(SCN)](n) (7 alpha-SCN), [Cu-2(L4-4)(SCN)](n) (7 beta-SCN), and [Cu-2(L4-4)-(N3)](n) (7 alpha-N-3). These structures are based on a series of isomeric pyridylpyrazole ligands, namely, 3,5-bis(3-pyridyl)-1H-pyrazole (HL3-3), 3-(3-pyridyl)-5-(4-pyridyl)-1H-pyrazole (HL3-4), and 3,5-bis(4-pyridyl)-1H-pyrazole (HL4-4), and their structural features range from 1-D (1), 2-D (2), and 3-D noninterpenetration (3), to 3-D 2-fold interpenetration (4 and 5), to 3-D self-catenation (6 and 7), exhibiting a trend from simple to complex with dimension expansion and an interpenetrating degree increase. The five most complex structures (6 and 7) with self-catenated networks are based on 2-fold interpenetrated networks linked via appropriate second ligating spacers (Cl-, Br-, SCN-, and N-3(-)), representing a strategy to construct self-catenated coordination polymers through cross-linking interpenetrated frameworks. Moreover, these complexes exhibit strong photoluminescence, which is mainly ascribed to Cu-I-related charge transfers (MLCT, MC, and MMLCT) regulated by the electronic properties of halogen or pseudohalogen. The topological evolution and, luminescence variation presented in this work open an avenue to understanding the luminescence origin and the structure property relationship of luminescent coordination polymers.