A recent study unveiled the potential of acrylamide-based stimulus-responsive hydrogels for volatile organic compound detection in gaseous environments. However, for gas sensing, a large surface area, that is, a highly porous material, offering many adsorption sites is crucial. The large humidity variation in the gaseous environment constitutes a significant challenge for preserving an initially porous structure, as the pores tend to be unstable and irreversibly collapse. Therefore, the present investigation focuses on enhancing the porosity of smart PNiPAAm hydrogels under the conditions of a gaseous environment and the preservation of the structural integrity for long-term use. We have studied the influence of polyethylene glycol (PEG) as a porogen and the application of different drying methods and posttreatment. The investigations lead to the conclusion that only the combination of PEG addition, freeze-drying, and subsequent conditioning in high relative humidity enables a long-term stable formation of a porous surface and inner structure of the material. The significantly enhanced swelling response in a gaseous environment and in the test gas acetone is confirmed by gravimetric experiments of bulk samples and continuous measurements of thin films on piezoresistive pressure sensor chips. These measurements are furthermore complemented by an in-depth analysis of the morphology and microstructure. While the study was conducted for PNiPAAm, the insights and developed processes are general in nature and can be applied for porosity engineering of other smart hydrogel materials for VOC detection in gaseous environments.