Photothermal therapy in the treatment of malignant tumors had attracted extensive attention owing to unique non-invasive and low-toxicity characteristics. Herein, aza-BDOIPY scaffold (NEt-azaBDP) was employed to construct a novel molecule using the duplex design strategies of diethylamino substitute and tert-butyl introduction. Self-assembly NEt-azaBDP nanoparticles (NEt-azaBDP NPs) had no fluorescence but produced heat energy via non-radiative transition, owing to the combination of the intramolecular charge transfer (ICT) by diethylamino groups and the free rotation tert-butyl segment. The photothermal conversion efficiency can reach 51.2 % under light irradiation. NEt-azaBDP NPs effectively kill glioma cells when exposed to light, and significantly impede the migratory and proliferation of gliomas. The observed therapeutic effects are attributed to the impairment of mitochondria in gliomas based on mitochondrial bioenergetic analysis. This provides a good strategy for the design of NEt-azaBDP NPs with the potent photothermal therapeutic effects which augur well for the prospective clinical applications for gliomas.