The NIR-I absorption and NIR-II luminescence of TPE-BBT were ideal for the NIR-II photo-and chemiluminescence imaging. TPE-BBT PLNPs were fabricated for blood vessel imaging in the mice model. The results showed that TPE-BBT showed a better SBR and imaging quality than those of TPA-BBT and commercially available ICG, indicating the high potential of TPE-BBT as a PL imaging agent.