Upon complexation with α-CD, the red fluorescence of TPE-Py was intensified and its total ROS generation was partially inhibited. Interestingly, the supramolecular assemblies of TPE-Pyα-CD accelerated type II ROS production significantly, which involved the consumption of intracellular oxygen to generate a high level of toxic singlet oxygen ( 1 O2). Inspired by this, such supramolecular complexes can result in a severe hypoxic microenvironment in solid tumor to facilitate hypoxia-responsive prodrug release. Then, the high-performance of TPE-Pyα-CD and PTX-NB were co-assembled into organic NPs with the aid of DSPE-PEG2000 for anticancer investigation. Benefitting from the outstanding PDT property and selfaccelerated chemotherapeutic prodrug, this supramolecular nanoplatform was used for bioimaging and antitumor treatment in vitro and in vivo with good biosafety. This synergistic strategy based on PDT and hypoxia-responsive prodrug helped to enhance the precision of Singlet oxygen ( 1 O2) generation. For 1 O2 detection indicated by 9,10-anthracenediylbis(methylene)-dimalonic acid (ABDA), the stock solution of ABDA (5 mM) was diluted to 50 µM in the sample solution of TPE-Py, TPE-Qu, TPE-Pyα-CD and TPE-Quα-CD (10 µM) in PBS. The absorption spectra of ABDA were monitored in a range of 320-420 nm after the solution was irradiated by white light irradiation (100 mW cm -2 ). The absorbance decrease of ABDA at 378 nm was recorded to indicate the decomposition rates of ABDA.