AbstractIn this research, we developed a novel and facile strategy to prepare aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s with pH and thermo responsiveness via phosphazene base (t‐BuP2) catalyzed oxa‐Michael addition polymerization of triethanolamine with ethylene glycol diacrylate at room temperature. UV–vis and fluorescence analyses results showed that the tertiary amine at branching point for hyperbranched poly(amino ether ester)s is very important to retain strong blue fluorescence of tertiary amine chromophore. Moreover, the hyperbranched poly(amino ether ester)s exhibit an aggregation caused quenching (ACQ) fluorescence, solvent induced red‐shifted emission, molecular weight, and temperature dependent emission characters. More interestingly, the hyperbranched poly(amino ether ester)s show extreme acid induced quenching fluorescence phenomenon, and also display good water solubility, specific recognition of Fe3+ ion, low cytotoxicity, and bright cell imaging, which could serve as a microenvironment‐responding fluorescent probe for application in chemical sensing, cell imaging, drug delivery, or disease diagnostics. This research provides a versatile method for the preparation of stimuli‐responsive aliphatic tertiary amine chromophore polymers, and supplies ideas for researchers to explore other unconventional fluorescent polymers for application.