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Metal–organic frameworks (MOFs) are unique microporous materials being explored for a wide range of applications. Their porosity and high surface areas can readily be exploited for guest–host interactions, separations, and photochemical catalysis, but many suffer from poor charge separation and fast electron–hole recombination. Introducing structural defects, such as missing linkers or metal nodes, can create unsaturated metal sites and alter band structure, conductivity, and light absorption, improving photocatalytic performance. UiO-66-NH2 and MIL-125-NH2 are water-stable, visible-light-absorbing MOFs well suited for photocatalytic degradation of organic dyes. In this work, the influence of defect engineering on photocatalytic properties of MOFs was investigated using formic and acetic acid modulators with UiO-66-NH2 and variable temperature with MIL-125-NH2 during synthesis. The resulting materials were characterized by XRD, FTIR and SEM/EDS. Defect states were tracked using N2 adsorption/BET analysis and UV–Vis spectroscopy. Photocatalytic activity was evaluated by monitoring Rhodamine B (RhB) degradation in aqueous solution under simulated solar irradiation. It was found that increased temperature beyond 120 °C during synthesis promotes mesopore formation and decreases the bandgap in MIL-125-NH2, resulting in a more photoactive material. Defective MIL-125-NH2 synthesized at 150 °C showed the most defects and proved to be the best photocatalyst investigated in this study. Formic acid modulation in UiO-66-NH2 generated smaller crystallites that slightly increased the bandgap; however, the surface area decreased proportionally with the amount of formic acid used. The decreased surface area and observed enhancement in photocatalytic degradation of RhB suggest that formic acid introduces defects into the UiO-66-NH2 framework that enhance photocatalytic properties. UiO-66-NH2 treated with acetic acid resulted in larger crystals, increased bandgaps, and increased surface areas, suggesting that acetic acid simply modulates growth rather than imparting defects to the framework.