Controlled syntheses of phthalocyanine/benzoporphyrin hybrid structures have been achieved. We report a simple means for obtaining non-peripherally octaalkyl-substituted derivatives of tetrabenzotriazaporphyrin (TBTAP), tetrabenzodiazaporphyrin (TBDAP), tetrabenzomonoazaporphyrin (TBMAP) and tetrabenzoporphyrin (TBP) macrocycles by treating 3,6-dialkyl phthalonitriles with differing amounts of the Grignard reagent MeMgBr. This range of macrocyclic products is not obtained from corresponding reactions of a Grignard reagent with 4-substituted phthalonitriles, reported previously, or reaction of MeMgBr with a 4,5-dialkyl phthaloni-trile. Attempts to form a meso-substituted TBTAP from 3,6-dialkyl phthalonitriles by reaction with benzyl and long-chain alkyl Grignard reagents unexpectedly gave only the parent macrocycle unsubstituted at the meso position. The synthetic protocols are by far the most straightforward and convenient means to access these interesting, but scarcely studied, classes of material. The new series of substituted macrocyclic compounds, obtained as the metal-free and magnesium-and copper(II)-metallated derivatives, show trends in the UV/Vis spectra consistent with those predicted elsewhere by Kobayashi. Characterisation of the new families allows further trends to be identified as meso-nitrogen atoms are sequentially replaced by methine bridges, for example, the compounds provide novel examples of macrocyclic structures that show columnar mesophase behaviour. Single-crystal X-ray structure determinations have been obtained for three magnesium-metallated derivatives bearing eight hexyl substituents and constitute the first set of structural data obtained for such a series.