A sensitive silver substrate for surface-enhanced Raman scattering (SERS) spectroscopy is synthesized under multimode microwave irradiation. The microwave-assisted synthesis of the SERS-active substrate was carried out in a modified domestic microwave oven of 2450 MHz, and the reductive reaction was conducted in a polypropylene container under microwave irradiation with a power of 100 W for 5 min. Formaldehyde was employed as both the reductant and microwave absorber in the reductive process. The effects of different heating methods (microwave dielectric and conventional) on the properties of the SERS-active substrates were investigated. Samples obtained with 5 min of microwave irradiation at a power of 100 W have more well-defined edges, corners, and sharper surface features, while the samples synthesized with 1 h of conventional heating at 40 degrees C consist primarily of spheroidal nanoparticles. The SERS peak intensity of the approximately 1593 cm(-1) band of 4-mercaptobenzoic acid adsorbed on silver nanoparticles synthesized with 5 min of microwave irradiation at a power of 100 W is about 30 times greater than when it is adsorbed on samples synthesized with 1 h of conventional heating at 40 degrees C. The results of quantum chemical calculations are in good agreement with our experimental data. This method is expected to be utilized for the synthesis of other metal nanostructural materials.