It is found that the fluorescence of aliphatic poly(amido amine)s including linear and hyperbranched ones can be dramatically enhanced by simple aggregation of polymer chains, attributing to the formation of a variety of intra- and interchain clusters with shared lone-pair electrons and the restriction of intramolecular motions. Thanks to the combination of strong solid fluorescence and excellent biocompatibility, these non-conjugated polymers become promising candidates for bioimaging such as bacterial detection. This finding not only extends the aggregation-induced emission (AIE) systems from conjugated compounds to non-conjugated materials, which expands the bioapplication range of AIE systems, but also sheds light on the exploration of novel unconventional luminogens.