Influence of process parameters of resorcinol–formaldehyde xerogel manufacture on final gel structure was studied, including solids content, preparation/drying temperature, solvent exchange, and drying method. Xerogels produced using a range of solids content between 10 and 40 w/v% show improved textural character up to 30 w/v% with a subsequent decrease thereafter. Preparation/drying temperature shows a minimal threshold temperature of 55 °C is required to obtain a viable gel structure, with minimal impact on gel properties for further thermal increase. Improving the solvent exchange method by splitting the same amount of acetone used in this phase over the period of solvent exchange, rather than in a single application, shows an increase in total pore volume and average pore diameter, suggesting less shrinkage occurs during drying when using the improved method. Finally, comparing samples dried under vacuum and at ambient pressure, there seems to be less shrinkage when using vacuum drying compared to ambient drying, but these changes are insubstantial. Therefore, of the process parameters investigated, improved solvent exchange seems the most significant, and it is recommended that, economically, gels are produced using a solids content of 20 w/v% at a minimum temperature of 55 °C, with regular solvent replenishment in the exchange step, followed by ambient drying.