We report, for the first time to the best of our knowledge, a systematic study to relate the laser action from BODIPY dyes, doped into monolithic hybrid matrices, with the synthetic protocols of the final materials prepared via sol‐gel. To this aim, the influence of both the hydrolysis time, increased in a controlled way, and the nature of the neutralization agent (pyridine, 3‐amino‐propyltriethoxy‐silane (APS), N‐3‐(trimethoxysilyl)propyl‐ethylene diamine (TSPDA), and N1‐3‐(trimethoxysilyl)propyl‐ diethylene triamine (TSPTA) on the laser action of PM567, incorporated into hybrid matrices based on copolymers of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA), with methyltriethoxysilane (TRIEOS) as inorganic precursor, was analyzed. The presence of the amine‐modified silane TSPDA as neutralization agent, which is able at the same time to be anchored to the inorganic network enhancing the inorganic‐organic compatibility through the matrix interphase, and utilization of hydrolysis times lower than 10 minutes, increased significantly the lasing efficiency and photostability of dye. The extension of this study to the laser behavior of BODIPY dyes embedded in other different hybrid materials based on hydrolyzed‐condensed copolymers of MMA with 3‐(trimethoxysilyl)propyl methacrylate (TMSPMA) in a 1/1 volumetric proportion, validates the generalization of the above conclusions, which provide guides for the optimization of the synthesis of organic‐inorganic hybrid materials with optoelectronic innovative applications independently of their composition. The direct influence of the synthetic protocol on the design and development of organic/inorganic hybrid materials with advanced and innovative applications, especially in the optoelectronic fields, is fully assessed. The control of both the neutralization reaction and the hydrolysis time is found to be a determining factor for the enhancement of the laser action of dyes incorporated into hydrid‐matrix active media for solid‐state dye lasers.