Melamine‐formaldehyde (MF) foam, while intrinsically flame retardant, necessitates further refinement to meet stringent fire safety standards, particularly in terms of heat release rate and thermal stability. In this study, an innovative approach was adopted wherein an inorganic substance, potassium water glass (WG), was employed to create an encapsulation layer on the surface of the MF foam structure via a straightforward dip‐coating technique. The composite foam underwent a comprehensive analysis of its structure and flame retardant characteristics, using test evaluations such as micro‐scale combustion calorimeter (MCC) testing, cone calorimeter testing (CCT), and thermogravimetric‐Fourier infrared spectrometer (TG‐IR) assessments. It was found that the even coating of WG on the MF foam surface profoundly enhanced the foam's structural integrity. Utilizing the shielding properties of this inorganic layer, the hybrid foam's thermal stability experiences a remarkable augmentation. The peak of heat release rate (pHRR) and the total heat release rate (THR) of the MF foam experienced an impressive reduction of 85.2% and 78.8%, correspondingly. Notably, this advancement is concomitant with a substantial decrease of 39.2% in the total smoke release (TSR) and a notable amelioration in mechanical characteristics. Such developments undeniably broaden their application horizons across diverse domains.