A straightforward coassembly strategy was developed for the preparation of polymeric nanoparticles driving by the intermolecular hydrogen bond between neutral poly(2-methyl-2-oxaozline) (PMeOx), tannic acid (TA) and doxorubicin hydrochloride (Dox). The occurrence of the hydrogen-bonding amongst the different functionalities within the formed nanoparticles was verified by infrared (IR) spectroscopy. Scanning electron microscopy (SEM), dynamic light scattering (DLS), UV-vis absorption and photoluminescent measurements indicated the rapid formation of uniform and water dispersible/stable nanoparticles. The relative poor stability of PMeOx-TA-Dox in fetal bovine serum (FBS) solution enabled the rapid separation of Dox and PMeOx-TA, facilitating the release of Dox and its entrance into cellular nuclei as revealed by confocal laser scanning microscopy (CLSM). The presented strategy may provide an efficient altative for the construction of multifunctional nanomedicines.