AbstractA series of luminescent frameworks was synthesized from the selective combination of aggregation induced emission (AIE)‐linker tetra‐(4‐carboxylphenyl)ethylene (H₄TCPE) and Zn²⁺. Complex 1 was formed by the close packing of Zn‐TCPE hinge, and isostructural complexes 2–5 were constructed by the linkage of Zn‐TCPE layer and pillar ligands. These complexes exhibit highly efficient multiphoton excited photoluminescence (MEPL) and concomitant third‐harmonic generation (THG). The multiphoton absorption (MPA) parameters of 1 are superior to other multiphoton emission materials including the perovskite nanocrystals. The incorporation of pillar linkers slows down the charge transfer between layers of Zn‐TCPE, and the aromatic core of pillar linkers has a great influence on the MPA performance of the corresponding frameworks.