<p>Nonlinear optical (NLO) materials are essential for the advancement of ultrashort laser pulses, optoelectronics, and high-speed optical communications. Improving the linear and nonlinear optical (NLO) properties of perylenediimide derivative, N,N’-di(2-(trimethylammonium iodide) ethylene) perylenediimide (TAIPDI) is essential for advanced photonic and optoelectronic applications. In this study, we investigate the NLO properties of a TAIPDI, immobilized within two zirconium-based metal-organic frameworks (MOFs): UiO-66 and UiO-66-NH₂. Using femtosecond laser pulses, we observed enhanced NLO responses in the MOF-dye composites compared to the TAIPDI dye. Characterization techniques, including steady-state absorption and fluorescence spectroscopy, revealed stronger interactions between TAIPDI and the amino-functionalized UiO66-NH₂ compared to UiO-66. Key NLO parameters were measured, including nonlinear refractive index (<i>n</i>₂), nonlinear absorption (NLA) coefficient (β), and third-order NLO susceptibility (χ⁽³⁾). The results demonstrated: (i) Both TAIPDI-UiO-66 and TAIPDI-UiO66-NH₂ exhibited significantly higher NLA and NLR coefficients compared to the free TAIPDI dye. (ii) TAIPDI-UiO66-NH₂ composite showed the most pronounced NLO enhancement, with <i>n</i>_<i>2</i> approximately 2.5 times higher than that of TAIPDI-UiO-66. (iii) The observed NLA behavior was attributed to RSA. (iv) The incorporation of TAIPDI into both MOFs resulted in significantly improved optical limiting properties. (v) TAIPDI-UiO-66 and TAIPDI-UiO66-NH₂ exhibited 2PACS values of 2.78 × 10⁷ GM and 3.25 × 10⁷ GM, respectively. These results highlight the synergistic effects of MOF encapsulation and framework functionalization, positioning these composites as highly promising materials for advanced photonic devices and optical power limiting applications.</p>