Here, we report a novel AuAg nanoalloy embedded sheet-like β-Bi 2 O 3 (β-Bi 2 O 3 /Au 2 Ag 2) hierarchical microsphere for rapid, sensitive and selective detection of environment pollutants including o -dianisidine (o -diASD) and Hg2+ ions in environmental samples. [Display omitted] • The sheet-like β-Bi 2 O 3 /Au 2 Ag 2 was synthesized by in-situ reduction method. • High SERS activity originates from synergistic effect of AuAg and β-Bi 2 O 3. • Good selectivity, stability and repeatability for SERS analysis. • The practical applications were achieved for analysis of environment pollutants. In this paper, we report a novel surface-enhanced Raman spectroscopy (SERS) substrate based on hierarchical β-Bi 2 O 3 /Au 2 Ag 2 microspheres for rapid, sensitive and selective detection of environment pollutants including o -dianisidine (o -diASD) and Hg2+ in environmental samples. The sheet-like β-Bi 2 O 3 not only provides large specific surface areas for adsorption of molecules and AuAg, but also emerges as semiconductor matrix with chemical enhancement combined with AuAg with electromagnetic enhancement, making promising SERS activity. Particularly, the β-Bi 2 O 3 /Au 2 Ag 2 shows high SERS performance for 4-mercaptobenzoic acid and TMB with minimum detectable concentration of 0.1 μg/L with enhancement factor of 3.1 × 107 and 6.3 × 107, respectively. The density functional theory simulations were further adopted to explain the high SERS activity and selectivity for o -diASD and TMB. Finally, the β-Bi 2 O 3 /Au 2 Ag 2 was applied to direct detection of o -diASD, and indirect detection of Hg2+ by TMB marking in environmental samples. The linearity range of 0.5–200.0 and 0.2–500.0 μg/L with limit of detection of 0.2 and 0.07 μg/L for o -diASD and Hg2+ ions can be achieved, respectively. This method provides a novel strategy in designing and fabricating SERS substrates with high performance for rapid, sensitive and accurate analysis of environmental pollutants. [ABSTRACT FROM AUTHOR]