A new bismuth(III) phthalocyaninate complex with the formula of [BiPc]4[Bi6I11Cl11] has been obtained in the reaction of pure bismuth filings with phthalonitrile under a stream of iodine monochloride. The complex crystallises in the centrosymmetric space group of the triclinic system. X-ray single crystal analysis revealed that iodine and chloride atoms statistically occupy one of eleven positions of the halogen atoms. Two independent [BiPc]+ cations have similar non-planar conformation. The Bi cation linked to the four N-isoindole atoms of the Pc2− macroring is significantly displaced by 1.117(3)Å and 1.146(2)Å for Bi4 and Bi5, respectively, from the planes defined by those N atoms of the Pc macrocycles. Since bismuth prefers higher coordination number than four, the [BiPc] units interact with three halogen atoms of the [Bi6I11Cl11]4− counter-ion forming centrosymmetric [BiPc]4[Bi6I11Cl11] aggregates. The arrangement of these aggregates in the crystal is determined by the π–π interaction between the phthalocyaninate macrocycles forming the stacking structure along the [111] and [100] directions. The single-crystal conductivity measurements along the stacking [111] and [100] directions gave quite the same values of ∼2.5×10−7Ω−1cm−1 and ∼2.8×10−7Ω−1cm−1, respectively. Temperature dependence of the conductivity exhibits non-metallic character (dσ/dT>0). In addition the compound was characterised by the UV–vis spectroscopy.