This study reports the synthesis and characterization of three sets of macrocycle co-crystals with identical co-constituents but varying stoichiometric ratios (2:1, 1:1, and 2:3) and molecular packing modes. The co-crystals are constructed using a triangular pyrene-macrocycle and 1,2,4,5-tetracyanobenzene, exploiting exo-wall charge-transfer (CT) interactions. These co-crystals exhibit distinct and tunable emission properties, with emission peaks appearing at 575, 602, and 635 nm, covering yellow to red. X-ray diffraction and density functional theory (DFT) calculations reveal that the superstructure-property relationships are attributed to the formation of different ratios of charge-transfer transition states between the donor and acceptor motifs, resulting in red-shifted luminescence. The study highlights the potential of organic co-crystal engineering for fabricating multifunctional materials with tunable optical properties.This study reports the synthesis and characterization of three sets of macrocycle co-crystals with identical co-constituents but varying stoichiometric ratios (2:1, 1:1, and 2:3) and molecular packing modes. The co-crystals are constructed using a triangular pyrene-macrocycle and 1,2,4,5-tetracyanobenzene, exploiting exo-wall charge-transfer (CT) interactions. These co-crystals exhibit distinct and tunable emission properties, with emission peaks appearing at 575, 602, and 635 nm, covering yellow to red. X-ray diffraction and density functional theory (DFT) calculations reveal that the superstructure-property relationships are attributed to the formation of different ratios of charge-transfer transition states between the donor and acceptor motifs, resulting in red-shifted luminescence. The study highlights the potential of organic co-crystal engineering for fabricating multifunctional materials with tunable optical properties.