In this work, we report the hot-injection synthesis of Cs3ZnCl5 colloidal nanocrystals (NCs) with tunable amounts of Cu+ and Mn2+ substituent cations. All the samples had a rodlike morphology, with a diameter of ∼14 nm and a length of ∼30–100 nm. Alloying did not alter the crystal structure of the host Cs3ZnCl5 NCs, and Cu ions were mainly introduced in the oxidation state +1 according to X-ray photoelectron and electron paramagnetic resonance spectroscopies. The spectroscopic analysis of unalloyed, Cu-alloyed, Mn-alloyed, and Cu, Mn coalloyed NCs indicated that (i) the Cs3ZnCl5 NCs have a large band gap of ∼5.35 eV; (ii) Cu(I) aliovalent alloying leads to an absorption shoulder/peak at ∼4.8 eV and cyan photoluminescence (PL) peaked at 2.50 eV; (iii) Mn(II) isovalent alloying leads to weak Mn PL, which intensifies remarkably in the coalloyed samples, prompted by an energy transfer (ET) process …