The core of the surface-enhanced Raman spectroscopy (SERS)-based techniques for dynamic monitoring is to realize rapid and reversible adsorption. Herein, the integration technology of electro-enhanced adsorption, solid-phase microextraction, and surface-enhanced Raman spectroscopy (EE-SPME-SERS) was developed to obtain sensitive, ultrafast, and reversible SERS response toward in situ monitoring of pharmaceuticals and personal care products (PPCPs). In the EE-SPME-SERS method, a roughened Ag fiber with Au modification (r-Ag/Au fiber) was used as the SERS substrate, SPME sorbent, and working electrode. The r-Ag/Au fiber displayed good SERS sensitivity, ultrahigh photostability, and adsorption properties. The adsorption efficiency of benzidine was 76 times accelerated in EE-SPME-SERS compared to that in static adsorption. The whole process of "sampling and detection" in EE-SPME-SERS can be finished within 1 s. Reversible adsorption and desorption can be achieved in situ by switching the direction of electric field, and the regeneration process takes only a few minutes. Simulated release of benzidine from household wastewater was in situ and dynamically monitored using this strategy. EE-SPME-SERS was proved universal for ionized PPCPs and can detect multicomponents simultaneously. In addition, EE-SPME-SERS showed very good analytical properties. Great potential of EE-SPME-SERS can be expected in environmental monitoring.