The combinatorial functionalization in a single molecular framework by structural integration utilizing multiple functional materials to create predefined structural morphology and multistimuli-responsive smart materials has attracted intensive attention. Herein, we constructed intrinsically porous and dual responsive supramolecule, TeDA, by introducing a photopolymerizable diacetylene template (10,12-pentacosadiynoic acid) to the sterically rigid tetrahedral tetraphenylmethane (TPM) core. The self-assembled monomeric TeDA is transformed into the covalently cross-linked blue-phase polydiacetylene (TePDA) by UV irradiation (UV 254 nm). The BET measurement and examination of SEM images confirm the mesoporous characteristic for TeDA/PDA. Very interestingly, the blue-phase TePDA produces a naked-eye detectable colorimetric response to heat and VOCs (liquid and vapor phase). Most importantly, TePDA exhibits reversible thermochromism and excellent colorimetric response to chloroform vapors. To signify the structural influence of TPM on material properties, we also studied non-TPM derivatives. The TeDA/PDA integrated system demonstrates potential applications in developing multistimuli-responsive sensors.