The crystal structure of [C₆H₄OCH₃NH₃]₂BiCl₅ was determined at room temperature. The compound crystallized in the following monoclinic space group: P2₁/c. The unit-cell dimensions are: a = 12.318(5), b = 21.486(5), c = 8.001(5)Å, β = 83.520(5)° with Z = 4. Its crystal structure was determined and refined down to R = 0.0365. The structure of this compound consists of corrugated layers of BiCl₅^2- chains in which slightly distorted [BiCl₆]^3- octahedral sharing two cis vertices are interconnected into chains separated by layers of organic [C₆H₄OCH₃NH₃]⁺ cations. These chains are themselves interconnected by means of the N-H…Cl hydrogen bonds, forming a three-dimensional network.