The green thionitrosyl complex [Cr(OH₂)₅(NS)]²⁺ was isolated in solution by hydrolysis of  [Cr(NCCH₃)₅(NS)]²⁺. The optical absorption spectra of both compounds are dominated by a band with vibrational progression around 600 nm assigned as a {d_yz,zx,p*(NS)} ¿ {p*(NS),d_yz,zx}* transition. The optical data indicate that the NS ligand is a weaker p-acceptor than the NO ligand. The EPR parameters of [Cr(OH₂)₅(NS)]²⁺ were determined: g_iso, g_¦ and g_-: 1.96515, 1.92686(5) and 1.986860(8); A_iso(⁵³Cr), A_¦(⁵³Cr) and A_-(⁵³Cr): 25.3´10^-4, 38´10^-4 and 18.5´10^-4cm^-1; A_iso(¹⁴N), A_¦(¹⁴N) and A_-(¹⁴N): 6.5´10^-4, 2.81´10^-4 and 8.346(12)´10^-4 cm^-1.