Because of sulfite's potential toxicity, there is a growing concern about detecting and controlling its concentration in foods, alcoholic beverages, pharmaceuticals, and environmental samples to ensure public health. A branched polyethyleneimine-coated silver nano-star (AgNS@PEI) surface-enhanced Raman scattering (SERS) substrate was synthesized in this study for use as a sensitive, simple, rapid, stable, and reproducible non-destructible sulfite detection analytical technique. The seed morphology of the nano-star was created by using hydroxylamine (NH2OH) solution as a primary reducing agent, followed by a slow secondary reduction by trisodium citrate dihydrate (HOC(COONa)(CH2COONa)2 2H2O), resulting in the complete growth of the silver nano-star. For extra stability and selective absorption of sulfur dioxide from the headspace extraction of SO2 from sulfites, the nano-stars were thin coated with branched polyethyleneimine (b-PEI). The results showed that the thin-coated plasmonic substrates selectively absorb sulfur dioxide molecules, allowing sulfites in beer samples to be detected with a detection limit of 0.48 mg/L. Furthermore, the PEI-coated silver nano-star demonstrated increased stability and reproducibility, allowing for longer use of the substrate. Recovery experiments with recovery rates ranging from 95 to 112% and relative standard deviations ranging from 1.55 to 8.1% demonstrated that headspace extraction, selective SO2 absorption by the synthesized substrate, and subsequent SERS detections were reliable and valid for practical applications. Finally, this study developed an SO2-sensitive, selective, and robust Si@AgNS@PEI substrate for effective SERS detection and monitoring of sulfite levels in real-world environmental samples.