The possibility of crystallizing silicalite-1 (MFI) from the pore walls of as-synthesized MCM-41 via steam-assisted crystallization (SAC) was thoroughly investigated. A kinetic study was conducted through the impregnation of as-synthesized MCM-41 with the structure-directing agent tetrapropyl-ammonium hydroxide (TPAOH). Materials obtained after different SAC treatment times (1–288 h) were characterized by XRD, nitrogen physisorption at 77 K, TGA/DTA, and SEM. The achieved results allowed us to conclude that during SAC treatment, rapid destruction of the hexagonal mesophase occurs with the enlargement of mesopores, probably by their coalescence, until achieving non-porous amorphous silica. Only thereafter is the crystallization of the MFI phase evidenced through the development of micron-sized (>10 µm) MFI structured crystals. This study suggests the probable practical impossibility of even partial crystallization of the pore walls of mesoporous materials by SAC.