New liquid-crystalline materials were prepared by self-assembly driven by halogen bonding between a range of 4-alkoxystilbazoles, 4-alkyl-, and 4-alkoxy-substituted pyridines as halogen-bonding acceptors, and substituted derivatives of 4-iodotetrafluorophenyl as halogen-bonding donors. Despite the fact that the starting materials are not mesomorphic, the dimeric, halogen-bonded complexes obtained exhibited nematic and SmA phases, depending on the length of the alkyl chains present on the components. The modularity of this approach also led to new chiral mesogens starting from non-mesomorphic chiral compounds.