The widespread use of surfactants and unregulated treatment of environmental media make them well-known environmental pollutants. It is of great significance to develop an effective discriminative sensor that can distinguish various surfactants, especially among anionic surfactants. In the present work, a dual-chromophorebased fluorescent probe was designed and synthesized, where pyrene and rhodamine were used as the signaling units and oligoethoxyl group used as a linker. The introduction of two chromophores was to increase the capacity of multi-wavelength cross-reactivity. Fluorescence measurements revealed that the probe could selectively recognize anionic surfactant SDS over cationic DTAB, neutral Tween 20 and zwitterionic SB3-10 by exhibiting extra rhodamine emission accompanied with pyrene emission. Moreover, the varied fluorescence emission of pyrene monomer, pyrene excimer, and rhodamine empowered the probe with multiple-wavelength cross-reactive responses to different anionic surfactants. The combination of the two ratio signals of pyrene monomer and excimer to rhodamine can generate specific recognition pattern for a particular anionic surfactant and provide a two-dimensional scattering plot for differentiating different anionic surfactants including SDS, SDBS, SDeS, SDSO, SDeSO, and AOT.