Our FRAME enables high-resolution structural characterization, providing crucial feedback for controlling structural arrangements and rationally designing materials for specific applications. Using this approach, we discovered that the unit cell and crystallinity of non-equilibrium OM structures can be manipulated by adjusting the laser focus position relative to the assembly's formation site. This adjustment alters the irradiation area and power density, resulting in concentric circle, cubic, or hexagonal crystal structures. These insights could only be obtained with FRAME, making it a key tool for the rational design of non-equilibrium assemblies. Moreover, our results provide the first detailed structural insight into small nanoparticle assemblies. Although previous studies indicated the formation of such assemblies, the exact structural details were unclear due to the limitations of optical microscopy and the inability to apply other characterization methods. Our FRAME has revealed that smaller nanoparticles exhibit more chaotic arrangements, lacking clear crystalline patterns. This can be attributed to two factors: smaller particles have higher diffusion coefficients, leading to increased entropy and a greater energy requirement to maintain order. Additionally, the light-matter interactions driving the assembly process, such as multiple scattering, scale with particle volume and these forces are significantly weaker in smaller particles. This challenge has led recent optical matter studies to focus on metallic particles, which have much stronger light-matter interactions due to their plasmonic properties. Non-equilibrium colloidal self-assemblies are particularly intriguing because, unlike their equilibrium counterparts, they can be dynamically tuned, reconfigured, and exhibit unique collective behaviors such as flocking, swarming, or propagating waves. These behaviors involve interactions within the colloids and with their surrounding medium, making them ideal, controllable model systems paving the way for intelligent swarming nanorobots. Our FRAME allows for high-resolution characterization of these transient structures and can be integrated with other techniques. By making the assemblies permanent, it also enables the exploitation of their properties for applications, which may not be possible when the structures rapidly change configurations.