This paper introduces an instantaneous and robust strategy for bonding a variety of non-silicon substrates such as thermoplastics, metals, an alloy, and ceramics to poly(dimethylsiloxane) (PDMS) irreversibly, mediated by one-step chemical modification using a mercaptosilane at room temperature followed by corona treatment to realize heterogeneous assembly also at room temperature. The mercapto functional group is one of the strongest nucleophiles, and it can instantaneously react with electrophiles of substrates, resulting in an alkoxysilane-terminated substrate at room temperature. In this way, prior oxidation of the substrate is dispensed with, and the alkoxysilane-terminated substrate can be readily oxidized and irreversibly bonded with oxidized PDMS at room temperature. A commercially available Tesla coil was used for surface oxidation, replacing a bulky and expensive plasma generator. Surface characterization was conducted by water contact angle measurement and X-ray photoelectron spectroscopy (XPS) analysis. A total of fifteen non-silicon substrates including polycarbonate (PC), two types of poly(vinylchloride) (PVC), poly(methylmethacrylate) (PMMA), polystyrene (PS), polyimide (PI), two types of poly(ethylene terephthalate) (PET), polypropylene (PP), iron (Fe), aluminum (Al), copper (Cu), brass, alumina (Al₂O₃), and zirconia (ZrO₂) were bonded successfully with PDMS using this method, and the bond strengths of PDMS–PMMA, PDMS–PC, PDMS–PVC, PDMS–PET, PDMS–Al, and PDMS–Cu assemblies were measured to be approximately 335.9, 511.4, 467.3, 476.4, 282.2, and 236.7 kPa, respectively. The overall processes including surface modification followed by surface oxidation using corona treatment for bonding were realized within 12 to 17 min for most of the substrates tested except for ceramics which required 1 h for the bonding. In addition, large area (10 × 10 cm²) bonding was also successfully realized, ensuring the high reliability and stability of the introduced method.