Near-infrared (NIR) persistent luminescence nanoparticles (PLNPs) showed great potential for bioimaging due to their integration of non-in situ excitation and deep tissue penetration. However, PLNPs are often introduced with Cr 3+ ions as the NIR emission centers. Herein, we report Cr-free Bi 2 Ga 3.985 O 9 :1.5% Fe 3+ (BGF), with Fe 3+ ions as the NIR emission centers. BGF under 310 nm excitation exhibited NIR afterglow emission at 794 nm in the first biological imaging window (650− 950 nm), with the afterglow duration of 3 h. BGF was grafted with hydroxyl groups and then polydopamine (PDA) for the integration of indocyanine green (ICG) through π−π stacking and hydrophobic interactions, as the PLNP−PDA−ICG composite. Bi in the composite, as a heavy atom element, exhibits computed tomography (CT) contrast capacity, while PDA is a photothermal agent, and ICG is excited to produce reactive oxide species for photodynamic therapy. The afterglow/CT dual-modality imaging-guided photothermal/photodynamic combination therapy was validated with in vitro/vivo imaging and therapeutic applications. This work provides the Cr-free PLNP composite for drug-free theranostics with a low toxicity.