In summary, our current research has facilitated the development of a concept of light-assisted dominant photothermal effect for synthesizing and assembling of MOFs. The light-assisted synthesis utilizes a molecular photothermal complex to achieve a relatively high temperatures (120 °C) for synthesis, and thus has potential to be incorporated into the repertoire of existing photothermal materials for practical applications. The distinctive photothermal activation of cobalt's molecular complex by specific light wavelengths (520 nm or 660 nm) results in the formation of Co-DHBDC assemblies or rods depending on activation wavelength. Additionally, we demonstrated the versatility of using photothermal activation through orthogonal activation in operando, which surpasses the capabilities of regular conventional heating methods. The insights gained from this study were leveraged to introduce palladium nanoparticle functionality to the synthesized structures. A deeper understanding of the dynamics between light to heat converters within the reaction enabled control over the assembly of Co-DHBDC simply by adjusting nanoparticle concentrations. Naturally, we aim to expand upon this knowledge and leverage the assembled structures, whether functional or nonfunctional, for various chemical reactions.