This study reports three sets of macrocycle co-crystals with distinct stoichiometric ratios (2:1, 1:1, and 2:3) and molecular packing modes, constructed using a triangular pyrene-macrocycle (Pe[3]) as the donor and 1,2,4,5-tetracyanobenzene (TCNB) as the acceptor. The co-crystals exhibit tunable emission properties, with emission peaks at 575, 602, and 635 nm, corresponding to yellow, orange, and red luminescence. The emission characteristics are influenced by the D-A ratios and the formation of different charge-transfer transition states between the donor and acceptor motifs. X-ray diffraction and density functional theory (DFT) calculations reveal the superstructure-property relationships, showing that the red-shifted luminescence is attributed to the varying CT interaction ratios. The study highlights the role of solvent modulation in controlling the stoichiometry and molecular arrangement of the co-crystals. The results demonstrate that the structural diversity of the co-crystals is determined by the topology of the macrocycles, leading to tunable luminescence properties. The findings provide insights into the structure-CT interaction-based luminescence relationship and offer a platform for the facile synthesis of solid-state multicolor CT luminescent materials. The study also shows that the solubility of TCNB and solvophobic forces play a critical role in determining the stoichiometric ratios of the co-crystals. The results indicate that the CT interaction between Pe[3] and TCNB is the dominant factor in the tunable photophysical properties of the co-crystals. The study presents a new approach for the design and synthesis of functional materials with tunable optical properties.This study reports three sets of macrocycle co-crystals with distinct stoichiometric ratios (2:1, 1:1, and 2:3) and molecular packing modes, constructed using a triangular pyrene-macrocycle (Pe[3]) as the donor and 1,2,4,5-tetracyanobenzene (TCNB) as the acceptor. The co-crystals exhibit tunable emission properties, with emission peaks at 575, 602, and 635 nm, corresponding to yellow, orange, and red luminescence. The emission characteristics are influenced by the D-A ratios and the formation of different charge-transfer transition states between the donor and acceptor motifs. X-ray diffraction and density functional theory (DFT) calculations reveal the superstructure-property relationships, showing that the red-shifted luminescence is attributed to the varying CT interaction ratios. The study highlights the role of solvent modulation in controlling the stoichiometry and molecular arrangement of the co-crystals. The results demonstrate that the structural diversity of the co-crystals is determined by the topology of the macrocycles, leading to tunable luminescence properties. The findings provide insights into the structure-CT interaction-based luminescence relationship and offer a platform for the facile synthesis of solid-state multicolor CT luminescent materials. The study also shows that the solubility of TCNB and solvophobic forces play a critical role in determining the stoichiometric ratios of the co-crystals. The results indicate that the CT interaction between Pe[3] and TCNB is the dominant factor in the tunable photophysical properties of the co-crystals. The study presents a new approach for the design and synthesis of functional materials with tunable optical properties.