limited by either the few choices of fluorophores [8,9] or the difficulty of aqueous modification, [10] which is especially true when NIR absorption and emission are required. [11,12] Moreover, the above-mentioned fluorophores mostly interact with analytes in a quenching scheme which can be easily affected in complex biological media such as cytoplasm or body fluid, making it more challenging to produce reliable in vivo lifetime signals. [13] Alternatively, thanks to the well-shielded 4f-4f transition, the lifetime of rare-earthdoped nanocrystals is less likely to fluctuate in those conditions once the emitters are well protected, [14][15][16] and NIR-emissive Tm 3+ , Er 3+ , Yb 3+ , or Nd 3+ has been widely applied in in vivo imaging. [17][18][19][20][21] The longer lifetime of rare-earth-doped nanocrystals also benefits background-free bioimaging as the short-lived autofluorescence can be filtered by time gate. [22][23][24] However, the commonly used rareearth-doped nanoparticles usually have to be passivated by an inert shell to prevent the quenching of activators and emitters (Yb 3+ , Tm 3+ ), [25][26][27][28][29] while the fluorescence energy transfer is most sensitive of distance. [30] This causes a dilemma; when a thicker shell increases the fluorescence intensity, the energy transfer efficiency inevitably drops. Therefore, it is necessary to design a luminescent lifetime probe which can take both the strong luminescence signal and the appropriate energy transfer distance into account thus meeting the requirements of detection in vivo. Recently, we reported a family of rare-earth nanocrystals with the absorption and emission at the same energy level, which has inspired our design. With time-domain filtering technique, the NIR light transducers have strong luminescence and high quantum yield compared to upconversion materials, NIR dyes, or quantum dots. [31] Based on these findings, a highly luminescent (182 times compared to core upconversion particles and 33 times compared to core-shell upconversion particles under low power density, as shown in Figure 3) and lifetime-responsive LRET nanocomposite was built for effective in vivo sensing (Figure 1). NaYF 4 :Tm nanocrystal, which absorbs and emits photons in the same transition ( 3 H 6 -3 H 4 ), was employed as the donors (Figure 1b). It was further combined with a commercially available IR-820 dye as acceptors, which has a specific response to ClO − , forming an NIR ClO − -responsive LRET nanocomposite. The lifetime was affected by the number of window (660-950 and 1000-1500 nm). Herein, this work reports a lifetimeresponsive nanocomposite with both excitation and emission in the NIR I window (800 nm) and lifetime in the microsecond region. The incorporation of Tm 3+ -doped rare-earth nanocrystals and NIR dye builds an efficient energy transfer pathway that enables a tunable luminescence lifetime range. The NaYF 4 :Tm nanocrystal, which absorbs and emits photons at the same energy level, is found to be 33 times brighter than optimized core-shell upconversi...