The shape of a drug delivery system impacts its behavior such as circulation time, accumulation, and penetration. Considering the advantages of functional dyes in bioapplications, we synthesize a class of nanoaggregates based on BF-azadipyrromethene (aza-BODIPY) dyes, which can realize long blood circulation and deep tumor penetration simultaneously through morphological transformation modulated by a near-infrared (NIR) laser. First, when the temperature increases, the wormlike nanofibers of the aza-BODIPY-1 aggregate, possessing a long blood circulation time, can be transformed into spherical nanoparticles, which are conducive to increasing the penetration in the solid tumor. Second, without any postmodification, the nanofibers exhibit an outstandingly narrow absorption band in the NIR spectral range, so that they possess ideal photothermal properties. Through 655 nm laser irradiation, the intrinsic photothermal effect causes a local temperature increase to ∼48 °C, realizing the transformation of 1-NFs to 1-NPs. Third, the morphological transformation is real-time detected by photoacoustic (PA) imaging. By monitoring the change of the PA signal at a specific wavelength, the deformation process of nanomaterials can be traced. Consequently, the morphology transformation of aza-BODIPY-based nanomaterials can simultaneously realize long blood circulation and deep penetration, resulting in the enhanced antitumor outcome.