This study demonstrates a novel strategy for colorimetric/surface-enhanced Raman scattering (SERS) dual-mode sensing of sulfur dioxide (SO₂) by coupling headspace sampling (HS) with paper-based analytical device (PAD). The smart and multifunctional PAD is fabricated with a vacuum filtration method in which 4-mercaptopyridine (Mpy)-modified gold nanorods (GNRs)-reduced graphene oxide (rGO) hybrids (rGO/MPy-GNRs), anhydrous methanol, and starch-iodine complex are immobilized into cellulose-based filter papers. The resultant PAD exhibits a deep-blue color with a strong absorption peak at 600 nm due to the formation of an intermolecular charge-transfer complex between starch and iodine. However, the addition of SO₂ induces the Karl Fischer reaction, resulting in the decrease of color and increase of SERS signals. Therefore, the PAD can be used not only as a naked-eye indicator of SO₂ changed from blue to colorless but also as a highly sensitive SERS substrates because of the SO₂-triggered conversion of Mpy to pyridine methyl sulfate on the GNRs. A distinguishable change in the color was observed at a SO₂ concentration of 5 μM by the naked eye, and a detection limit as low as 1.45 μM was obtained by virtue of UV-vis spectroscopy. The PAD-based SERS method is effective over a wide range of concentrations (1 μM to 2000 μM) for SO₂, and the detection limit for SO₂ is found to be 1 μM. The HS-PAD based colorimetric/SERS method is applied for the determination of SO₂ in wine, and the detection results match well with those obtained from the traditional Monier-Williams method. This study not only offers a new method for on-site monitoring of SO₂ but also provides a new strategy for designing of paper-based sensing platform for a wide range of field-test applications.

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