We present a rapid one-pot method for the synthesis of polymeric solid acid catalysts with carefully controlled properties using a dual polymerisation catalyst and sulfonation agent. Ten SHCPs were prepared with varying porous properties, acidity, and hydrophilicity by simply varying the initial catalyst to monomer ratio. These materials could be obtained in less than 24 h by combining the polymerisation and sulfonation steps into a one-pot procedure, significantly increasing the speed and ease of production. This had several advantages over conventional techniques, such as eliminating the need for metal-based polymerisation catalysts, dramatically reducing the amount of toxic solvents and sulfonation agents required, and hence lowering the cost of porous heterogeneous solid-acid catalysts. Comparison with equivalent materials produced via conventional routes showed that the properties obtained in SHCPs herein are superior with respect to both acidity and surface area. The SHCPs were applied to the acidcatalysed hydrolysis of cyclohexyl acetate to cyclohexanol. Conversions of up to 75% were measured, with all networks displaying excellent selectivity (>99%). Results strongly suggested that acidity is one of a number of important properties in the design of solid acid catalysts, with high acid densities even leading to reduced conversion rates. The ability to fine-tune polymer catalysts allows for the identification of key properties for further catalyst design and optimisation.