Abstract A silver‐ion‐coupled black phosphorus (BP) vesicle (BP Ve‐Ag + ) with a second near infrared (NIR‐II) window photoacoustic (PA) imaging capability was firstly constructed to maximize the potential of BP quantum dot (QD) in deeper bioimaging and diversified therapy. The embedded Ag + could improve the relatively large band gap of BP QD via intense charge coupling based on theoretical simulation results, subsequently leading to the enhanced optical absorption capability, accompanied with the occurrence of the strong NIR‐II PA signal. Guiding by NIR‐II PA bioimaging, the hidden Ag + could be precisely released with the disassembly of Ve during photodynamic therapy process and captured by macrophages located in lesion region for arousing synergistic cancer photodynamic/Ag + immunotherapy. BP Ve‐Ag + can contrapuntally kill pathogenic bacteria and accelerate wound healing monitored by NIR‐II PA imaging.