Hybrid xerogels RF/Si were synthesized by controlling the chemical variables involved in the polymerization process (i.e., molar ratios, dilution ratio, catalysts, etc.) and evaluated as insulator materials. Higher insulating performances were recorded for these hybrids compared with their counterparts made from only one of their components (i.e., RF or Si xerogels with similar porous characteristics). The analysis of chemical and structural features correlated with heat transfer methods was useful in understanding the sum of contributions involved in the thermal conductivity of RF/Si xerogels. Variables such as roughness and tortuosity can be used to improve the performance of xerogels from a different perspective. In this way, thermal conductivities of 25 mW/mK were achieved without lengthy process steps or special drying methods. Knowledge of material design and the use of microwave heating during the synthesis allowed us to approach a simple and cost-effective process. These results suggest that the hybrid materials developed in this work are a good starting point for the future of the massive production of insulation materials.