This article describes an effective probe PS for the detection of nitric oxide (NO), which can be monitored by both fluorescence and photoacoustic signals. PS contains two diphenylamine groups as electron donors conjugated to both ends of the molecule and benzothiadiazolediamine as electron acceptor and act as reaction moiety as well. The electron-rich aromatic diamine can react with NO under the aerobic condition to form a five-member ring, resulting in the increase of electron withdrawing of the acceptor moiety thus increase intramolecular charge transfer (ICT) in the Donor-Acceptor-Donor (D-A-D) structure. Probe PS has a fast fluorescence on-off response and excellent selectivity for NO over various reactive oxy-gen/nitrogen species (ROS/RNS) and AA, MGO. PS can also work as an effective photoacoustic (PA) probe towards NO with the off-on photoacoustic signal response due to large absorption change between the probe PS (368 nm) and its NO reactant PS-NO (568 nm). Further, probe PS was successfully applied to the detection of endogenous NO in RAW264.7 cells by fluorescence imaging and lipopolysaccharide-induced inflammation mice model by PA imaging.