The PbS-Bi₂S₃ join was studied up to 25 mole percent Bi₂S₃ by electron microscopy and diffraction. It was found that Bi₂S₃ can be incorporated into the PbS matrix by tropochemical twinning, forming isolated {113}_PbS microtwins, or after clustering of these defects, lamellar twinned regions. Only two known mineral members of the homologous series (lillianite Pb₃Bi₂S₆ and heyrowskyite Pb₆Bi₂S₉) were found to be stable in this part of the PbS-Bi₂S₃ join, while irregularly spaced twin bands within these two structures were observed where deviations in the PbS/Bi₂S₃ ratio from 6/1 and 3/1, respectively, took place. No ordered intergrowth members were found between heyrowskyite and lillianite. The difference between the PbS-Bi₂S₃ join and the analogous MnS-Y₂S₃ one was attributed to the lone pair of nonbonded electrons from the Bi³⁺ ions, which tends to concentrate these ions in the vicinity of the twin planes.