In this contribution, we present the synthesis and characterization of the mixed-anion halogenobismuthate(III) (CH3NH3)(6)BiI5.22Cl3.78 (MBIC) as an alternative lead-free perovskite-type semiconductor, and discuss its optical, electronic, and photovoltaic properties in comparison to the methylammonium bismuth iodide (CH3NH3)(3)Bi2I9 (MBI) compound. The exchange of iodide with chloride during synthesis leads to the formation of an orthorhombic A(6)BX(9)-type crystal structure (Cmma, No. 67) with isolated BiX6 octahedra and methylammonium chloride interlayers. The experimentally found optical indirect band gap of 2.25 eV is in good agreement with the calculated value of 2.50 eV derived from DFT simulations. The valence band maximum and the conduction band minimum were determined to be at -6.2 eV and -4.0 eV vs vacuum. Similar to MBI, thin films of MBIC are composed of microcrystalline platelets. Time-resolved photoluminescence measurements show electron transfer of MBIC to mesoporous TiO2. The photovoltaic behavior of both compounds is compared in solar cells with the following device architecture: glass/ITO/compact TiO2/mesoporous TiO2/MBIC or MBI/spiro-OMeTAD/Au. Despite the zero-dimensional structure of MBIC, a maximum power conversion efficiency of 0.18% and a high fill factor of almost 60% were obtained with this material as absorber layer. When stored under inert conditions, these solar cells show an excellent long-term stability over the investigated period of more than 700 days.