The coatings and surfaces are always subjected to mechanical damages, and microcracking can likely occur during handling, use, etc. These microcracks compromise the integrity of a material, which can lead to negative consequences. Conventional methods of surface repair are usually complicated and time-consuming procedures, which may not be effective enough over the service life of a surface having a short lifespan. Since the 1980s, demand for alternatives to surface reparation has led to the introduction and application of novel smart self-healing surfaces or, more specifically, the healing of microcracks to extend the life-span of polymeric components. This study aims to develop microcapsules that can be used as room-temperature self-healing agents in silicone-based matrices. A reactive silanol-terminated polydimethylsiloxane (PDMS) as the healing agent, was selected to ensure the homogeneity of the polymeric matrix and encapsulated in poly(melamine-urea-formaldehyde) shells through an in-situ emulsion polymerization technique. Dibutyltin dilaurate (DBTL) was encapsulated as the catalyst within the same type of polymeric shell. The synthesized microcapsules were characterized using Fourier-transform infrared spectrometry, optical microscopy, scanning electron microscopy, and differential scanning calorimetry. The analyses confirmed that the spherical microcapsules with an average size of 56 µm for PDMS-MUF microcapsules and 42 µm for DBTL-MUF microcapsules, with a shell wall thickness of 100–200 nm, and good thermal stability. Therefore, the two-component self-healing silicone composite was successfully developed using 10:1.2 wt.% PDMS:DBTL microcapsules within the silicone matrix. Scanning electron microscopy (SEM) confirmed the self-healing ability of the silicone matrix by observing the successful healing of microcracks at room temperature.