A typical and environment-friendly fluorescent polyamine-amine (PAMAM) features good compatibility and unique surface modification, while it is restricted by a low fluorescence property performance and an unclear fluorescence mechanism. In this work, we prepared blue fluorescent PAMAM polymer dots (PDs) via a simple hydrothermal method based on dichloromethane (DCM) and 2.0G PAMAM. The quantum yield achieved was 32.1%, which was 25 times stronger than that of 2.0G PAMAM due to the lone-pair electron leap of the amine groups, the aggregation of carbonyl groups, as well as the crosslinking induced by DCM inside the PAMAM. In addition, the fluorescent 2.0G PAMAM-DCM PDs show a great Fe3+ sensing property with the detection limit of 56.6 nM, which is much lower than the safety limits (5.36 μM) in drinking water, indicating its great potential for Fe3+ detection in aqueous media.