Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H¹L) and triphenylphosphine in 1 : 1 : 2 molar ratio yielded complexes of stoichiometry, [CuX(𝜂¹-S- H¹L)(Ph₃P)₂] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, ¹H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) Å, b = 13.027(5) Å, c = 16.269(5) Å, 𝛼 = 100.054(5)°, 𝛽 = 99.228(5)° and 𝛾 = 97.234(5)°. This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu₂Cl₂(𝜇₂-S-Hbtsc)₂(Ph₃P)₂]·2H₂O. The intermolecular H-bonding, Cl· · ·HC_ph, 2.733 Å and 𝜋 interactions, {CH_ph · · · 𝜋, 2.796; 2.776 Å} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl· · ·HC_ph, 2.896 Å H-bonding to form a 2D network.