New three-dimensional geopolymer materials based on illito-kaolinitic clay and phosphoric acid were synthesized. The effect of Si/P molar ratio on the geopolymers properties was studied. Raw, calcined clay, and geopolymers structures were investigated using XRD, IR spectroscopy, and SEM. The phosphoric acid-based geopolymers mechanical properties were evaluated by measuring the compressive strength. The Si/P molar ratio was found to increase with the increase of the compressive strength of the obtained geopolymers, which attained a maximum value at Si/P equal to 2.75. Beyond this ratio, the mechanical strength decreases. The XRD patterns of these geopolymers samples have proven that when the Si/P molar ratio decreases, the amorphous phase content increases. Besides, the structural analyses have revealed the presence of aluminum phosphate and Si-O-Al-O-P polymeric structure, whatever the Si/P molar ratio is (between 2.25 and 3.5). The obtained results have confirmed that the presence of the associated minerals such as hematite and quartz in the clay does not prevent the geopolymerization reaction, but the presence of illite mineral seems to have a modest contribution in the geopolymerization.