This study investigates the formation of microstructured macromaterials from thermo- and pH-sensitive microgels based on interpenetrating networks of poly-N-isopropylacrylamide (PNIPAM) and polyacrylic acid (PAA). Macromaterials are produced as a result of the deposition of microgel particles and subsequent crosslinking of polyacrylic acid subnetworks to each other due to the formation of the anhydride bonds during annealing. Since both PNIPAM and PAA are environment-sensitive polymers, one can expect that their conformational state during material development will affect its resulting properties. Thus, the influence of conditions of preparation for annealing (pH of the solution, the temperature of preliminary drying) on the swelling behavior, pH- and thermosensitivity, and macromaterial inner structure was investigated. In parallel, the study of the effect of the relative conformations of the IPN microgel subnetworks on the formation of macromaterials was carried out by the computer simulations method. It was shown that the properties of the prepared macromaterials strongly depend both on the temperature and pH of the PNIPAM-PAA IPN microgel dispersions. This opens up new opportunities to obtain materials with pre-chosen characteristics and environmental sensitivity.