Yellow crystals of Bi(SCN)₃·H₂O are obtained by reacting (BiO)2CO3 and HSCN in aqueous solution. X-ray diffraction on a single-crystal revealed a triclinic lattice (space group P1) with a = 843.6(2) pm, b = 920.4 (2) pm, c = 1210.7(2) pm, α = 109.16(3) °, β = 109.06(3) °, γ = 90.22(3) °, V = 832.8(3)·10 pm, and Z = 4. All thiocyanate anions bind with both ends to different cations. The coordination network expands in plane layers parallel (1 1 0). The water molecule coordinates one of the two independent Bi³⁺ cations. Dehydration sets in at 100 °C, followed by stepwise thermal decomposition to Bi₂S₃.