A new coordination polymer (CP) defined as [Cu₂Cl₂(EtS(CH₂)₄SEt)₄]_n (CP2) was prepared by reacting EtS(CH₂)₄SEt with CuCl in acetonitrile in a 1 : 2 stoichiometric ratio. The X-ray structure reveals formation of non-porous 3D material composed of parallel 2D-[Cu₂Cl₂S₂]_n layers of Cl-bridged Cu₂(μ-Cl)₂ rhomboids assembled by EtS(CH₂)₄SEt ligands. A weak triplet emission (Φ_e < 0.0001) is observed in the 400–500 nm range with τ_e of 0.93 (298 K) and 3.5 ns (77 K) as major components. CP2 is the only 2nd example of emissive thioether/CuCl-containing material and combined DFT/TDDFT computations suggest the presence of lowest energy M/XLCT excited states. Upon increasing the photon flux (i.e. laser power), a triplet–triplet annihilation (TTA) is induced with quenching time constants of 72 ps (k_Q = 1.3 × 10¹⁰ s⁻¹) and 1.0 ns (k_Q = 7.1 × 10⁸ s⁻¹) at 298 and 77 K, respectively, proceeding through an excitation energy migration operating via a Dexter process. Two distinct (I_o)^1/2 (I_o = laser power) dependences of the emission intensity are depicted, indicating saturation as the observed emission increases with the excitation flux. These findings differ from that previously reported isomorphous CP [Cu₂Br₂(μ-EtS(CH₂)₄SEt)₄]_n (CP1), which exhibits no TTA behaviour at 77 K, and only one (laser power)² dependence at 298 K. The ∼18-fold increase in k_Q upon warming CP2 from 77 to 298 K indicates a temperature-aided TTA process. The significant difference between the presence (slower, CP2) and absence (CP1) of TTA at 77 K is explained by the larger unit cell contraction of the former upon cooling. This is noticeable by the larger change in inter-rhomboid Cu⋯Cu separation for CP2.