To enhance the integration and practical applicability of the Raman detection system, silver nanocubes (Ag NCs) were synthesized using a polyol method. A liquid-liquid interface approach was employed to transfer a monolayer of Ag NCs "film" onto a SiO2 substrate, resulting in the fabrication of a highly sensitive and uniform surface-enhanced Raman scattering (SERS) substrate denoted as "Ag NCs@SiO2." The electromagnetic field distribution of various dimers on the Ag NCs@SiO2 was analyzed using finite difference time domain (FDTD) software. The results reveal that the electromagnetic enhancement effect is most pronounced in cube-cube dimers, indicating that Ag NCs exhibit superior localized surface plasmon resonance (LSPR) response due to their well-defined geometric regularity and sharp geometric angles. For Rhodamine 6G (R6G) probe molecules, the Ag NCs@SiO2 shows ultrahigh sensitivity, with a limit of detection (LOD) of 10-12 mol/L, and the enhancement factor (EF) can reach 1.4 × 1010. The relative standard deviation (RSD) at the main characteristic peaks is below 10%, demonstrating good consistency in substrate performance. In addition, the Ag NCs@SiO2 modified with hexanethiol exhibits high sensitivity, uniformity, and repeatability in detecting for pyrene, with the LOD of 10-8 mol/L and a minimum RSD of 6.09% at the main characteristic peak, and effective recognition capabilities for pyrene and anthracene in mixed solutions. Finally, chemisorption and physisorption strategies were prepared in optofluidic channels and experimentally compared, enabling real-time detection of the pyrene solution. This method can achieve a rapid detection and precise differentiation of polycyclic aromatic hydrocarbons in a water pollutant.