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Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants, which cause serious harm to human health and ecological environment. Thus, a low-cost membrane was developed for highly effective removal and rapid surface-enhanced Raman scattering (SERS) detection of PCBs by filling esterified-sawdust (CA-SD) modified with silver nanoparticles (AgNPs) into solid phase extraction (SPE) column. SD was first modified by an esterification cross-linking strategy and then AgNPs were anchored on the CA-SD to prepare highly sensitive and reproducible SERS substrates (AgNPs/CA-SD). Due to the contraction of the surface area of the CA-SD caused by drying, the gap between the AgNPs could be reduced, thereby generating a large number of hot spots and driving more target molecules into them to obtain the enhanced SERS signals. The AgNPs/CA-SD-based SPE membrane showed excellent SERS activity with an enhancement factor of 5.98 × 108 for the R6G analysis. The proposed SERS-active SPE membrane with functionalization of mercapto-β-cyclodextrin was further developed for the determination of PCB-77 and PCB-1 with the LODs of 1.43 × 10−9 M and 2.12 × 10−8 M, respectively. In addition, each PCB in the mixed sample could be quickly distinguished based on the characteristic peaks. The current research exhibits great potential for the simultaneous detection of multiple environmental contaminants and can meet the needs of on-site emergency detection. [Display omitted] • A low-cost sawdust-based SPE membrane was prepared through esterification and modification process. • The membrane could realize enrichment and high-sensitivity SERS detection of PCBs. • The membrane was capable of rapid analysis of the mixed PCBs samples. • This membrane is expected to be used for on-site rapid analysis of water pollution incidents. [ABSTRACT FROM AUTHOR]