Silica fillers have been a cornerstone in chemical technology due to their versatility, availability, and ease of integration into various formulations. Recent advancements, including chlorine-free synthesis of alkoxysilanes, have paved the way for alternative materials like polymethylsilsesquioxane (PMSSO). This study explores the structural evolution and properties of a hydrophobic PMSSO xerogel, synthesized through hydrolytic polycondensation of methyltriethoxysilane (MTEOS). PMSSO exhibits exceptional hydrophobicity, high specific surface area, and compatibility with polymer matrices, making it a promising filler for applications in rubber products, lubricants, and cosmetics. We developed a straightforward synthesis method for producing PMSSO xerogel that avoids toxic solvents and organochlorosilanes, ensuring safety and sustainability. The reaction conditions, particularly the amount of alkali and neutralization parameters, were found to significantly influence the properties of the final xerogels, such as specific surface area. Optimization of the synthesis parameters allow for obtaining PMSSO xerogels with a specific surface area about 600 m