Single crystals of non-peripherally alkyl-substituted macrocycle molecules, such as octahexylphthalocyanine (C6PcH(2)), octapentylphthalocyanine (C5PcH(2)), octahexyltetrabenzotriazaporphyrin (C6TBTAPH(2)), and their blends were prepared. The crystal structures of C6PcH(2) and C5PcH(2), which were determined by single-crystal X-ray structure analysis, were identified as monoclinic lattices, while that of C6TBTAPH(2) was identified as a triclinic lattice. Despite the similarity between the crystal structures of C6PcH(2) and C5PcH(2), the single crystals grown from the blended solutions of C6PcH(2) and C5PcH(2) were based on a triclinic lattice. On the other hand, in the case of the single crystals composed of C6PcH(2) and C6TBTAPH(2), another type of crystal structure did not appear. The crystal structures of these single crystals are discussed by taking the differences in the alkyl-substituent length and the core structure into consideration.