Heating a solid mixture of (NH4)3VS4, CuCl, PPh3, and NEt4Br at 100°C for 10 h and extraction with CH2Cl2 yielded [VS4(CuPPh3)4Br]·CH2Cl2. Crystallographic data: Triclinic, P¯1, a = 15.189(3), b = 20.093(6), c = 12.031(3) Å, α = 102.39(2), β = 100.05(2), γ = 82.86(2)°, V = 3517(3) Å3, and Z = 2. The configuration of the VS4Cu4Br core can be described as a distorted cubane with an additional face. The V atom has retained the tetrahedral geometry of the free [VS4]3− moiety. The four Cu atoms have three different coordination environments, strongly distorted tetrahedral, nearly trigonal planar, and strictly trigonal planar. The infrared, electronic, and 51V NMR spectra have also been reported.