An investigation into the dependence of the framework formation of coordination architectures on ligand spacers and terminal groups was reported based on the self-assembly of AgClO₄ and eight structurally related flexible dithioether ligands, RS(CH₂)_nSR (L_aⁿ, R = ethyl group; L_bⁿ, R = benzyl group, n = 1–4). Eight novel metal–organic architectures, [Ag(L_a¹)_3/2ClO₄]_n (1a), [Ag₂(L_a²)₂(ClO₄)₂]₂ (2a), [AgL_a³ClO₄]_n (3a), {[Ag(L_a⁴)₂]ClO₄}_n (4a), [AgL_b¹ClO₄]₂ (1b), [Ag(L_b²)₂]ClO₄ (2b), {[Ag(L_b³)_3/2(ClO₄)_1/2](ClO₄)_1/2}_n (3b) and [Ag(L_b⁴)_3/2ClO₄]_n (4b), were synthesized and structurally characterized by X-ray crystallography. Structure diversities were observed for these complexes: 1a forms a 2-D (6,3) net, while 2a is a discrete tetranuclear complex, in which the Ag^I ion adopts linear and tetrahedral coordination modes, and the S donors in each ligand show monodentate terminal and μ₂-S bridging coordination fashions; 3a has a chiral helical chain structure in which two homo-chiral right-handed single helical chains (Ag–L_a³–)_n are bound together through μ₂-S donors, and simultaneously gives rise to left-handed helical entity (Ag–S–)_n. In 4a, left- and right-handed helical chains formed by the ligands bridging Ag^I centers are further linked alternately by single-bridging ligands to form a non-chiral 2-D framework. 1b has a dinuclear structure showing obvious ligand-sustained Ag–Ag interaction, while 2b is a mononuclear complex; 3b is a 3-D framework formed by ClO₄⁻ linking the 2-D (6,3) framework, which is similar to that of 1a, and 4b has a single, double-bridging chain structure in which 14-membered dinuclear ring units formed through two ligands bridging two Ag^I ions are further linked by single-bridging ligands. In addition, a systematic structural comparison of these complexes and other reported AgClO₄ complexes of analogous dithioether ligands indicates that the ligand spacers and terminal groups take essential roles on the framework formation of the Ag^I complexes, and this present feasible ways for adjusting the structures of such complexes by modifying the ligand spacers and terminal groups.