Photothermal activation is a process wherein photons are transformed into localized heat within lightabsorbing materials, while the overall bulk temperature remains relatively low. Since the beginning of chemistry, researchers have noticed the importance of controlling temperature in any chemical process. Over the past years, the idea of utilizing photothermal materials to control temperature and introduce gradients to a reaction's heat profile has been growing, yet remains in large an unexplored strategy. Various types of nanomaterials exhibit photothermal properties with plasmonic nanostructures (e.g., Au, Ag etc.), and carbon-based materials being among the most prevalent. Each category of materials has its distinct features bringing to the table advantages and drawbacks depending on the relevant system's requirements. For example, plasmonic structures are highly efficient light-to-heat converters with tunable absorption wavelengths, however, to unlock their potential, complicated nanostructures of precious metals must be synthesized. In contrast, carbonbased photothermal agents are far less costly and have broad absorptions across the visible spectrum. Nevertheless both cases generally necessitate surface modifications for homogenous activation in solution. Molecular compounds can also convert light to heat through photoinduced non-radiative thermal relaxation. A classic example from the natural world is chlorophyll, a metallomacrocycle, used by plants to convert excess photon energy into heat among its other roles. Although there are reports on the photothermal activity of homogeneous solutions with compounds such as organic polymers and synthetic chromophores, they are restricted to low temperatures due to low photothermal conversion and stability concerns. At present, the primary focus of photothermal applications lies within the realm of biomedical fields, with limited exploration into synthetic processes, particularly those demanding elevated temperatures. In our work, we harness the photothermal capabilities of three different classes of converters (cobalt chloride molecular complex, cobalt metal organic framework, and palladium nanoparticles) to facilitate the synthesis of metal-organic frameworks (MOFs) and develop a novel pathway to their self-assembly. MOFs are characterized by their crystalline structures, comprising of metal ions or clusters linked by organic connectors, resulting in highly porous materials with extensive surface areas. The versatility of MOFs has spurred significant research across diverse fields, including gas storage and separation , drug delivery , sensing , catalysis , electronic devices , and membranes , making MOF synthesis an area of considerable interest. The photothermal approach was previously shown to enable the formation of intricate assemblies of metallic nanoparticles , herein we present a highly innovative application of this technique to achieve stable self-assemblies of MOFs. The assembly of colloidal MOF particles into micro or nano-superstructures is a powerful strategy to obtain advanced materials with improved properties. Nonetheless, effective routes to obtain stable these assemblies remain scarce and relatively unexplored, presenting opportunities for innovation. The few existing methods include assembly by capillary force , DNA hybridization , polymer matrix templating , electric field , and more recently liquid bridging . However, these techniques are often impeded with extensive surface functionalization, meticulous design, reaction control, and templating. In our work we uncover the versatility of the photothermal approach by studying the light assisted synthesis of cobalt-2,5-dihydroxyterephthalic acid MOF (Co-DHBDC) with different light-to-heat converters at two distinct wavelengths. Initially, the photothermal response of a homogeneous Co complex was utilized at 520 and 660 nm light to initiate the formation of individual MOF rods or their assembly depending on the wavelength. The molecular cobalt chloride complex proved to be a highly efficient and stable photothermal agent enabling remote control over the temperature and activation of the reaction. A comprehensive analysis of the assembly mechanism indicated that the newly formed MOF particles functioned as additional photothermal agents (PTAs) thus serving as a nucleus around which superstructures could grow. In addition, this hypothesis was tested by introducing a competing PTA in the form of palladium nanoparticles (PdNPs). Finally, the in-situ insertion of PdNPs to MOF superstructures was shown to be possible and wavelength specific by utilizing the photothermal method.