Casimir self-assembly (CaSA) is an interdisciplinary field that combines colloid chemistry, nanophotonics, and quantum electrodynamics. At room temperature in aqueous solutions, the micron flakes self-assemble to form Fabry-Pérot resonators with a tunable optical response in the visible spectral range. Despite recent advances, direct evidence linking these systems to quantum effects has been lacking. In this study, experimental and theoretical techniques investigating the effect of thermal fluctuations (TF) on these systems were used to address this issue. Optical microscopy and reflection spectroscopy were used to measure TF and experimentally map the Casimir-electrostatic potential, while a probabilistic model involving the Boltzmann factor provided theoretical explanations of the interaction potential. This approach confirms the presence of a quantum attractive Casimir force within the cavities and reveals the stability mechanisms and limits of CaSA tunability in surfactant-salt solu-tions. In addition, this study introduces a new optical approach for analyzing nanoscale interactions and broadens the potential of CaSA applications in advanced nanophotonic systems and colloidal and polaritonic chemistry.