The Raman detection of trace substances in complex oil is still a great challenge at present because of the strong disturbance of background activity and the suppression of intensity in spectra caused by complicated components. In this work, a simple and robust approach based on microdroplet liquid-liquid extraction for the real-time Raman spectroscopy monitoring of trace substances in complex oil is reported. Based on unbalanced chemical potentials between water and oil on a microfluidic chip, a target trace molecule is extracted from complex mineral oil to a water microdroplet. Benefiting from the real-time fluorescence intensities of fluorescein in a water microdroplet, the extraction performance is investigated and optimized. The optimal water microdroplet is implemented for the Raman detection of furfural in a complex mineral oil, a typical trace performance marker in electric power equipment, and this exhibits excellent sensitivity with a limit of detection (LOD) of 26 ppb. Compared to traditional detection technology for trace substances in complex oil (high performance liquid chromatography, HPLC), this method greatly simplified the process of measurement, reduced the volume of sample required, had a fast measurement time, and exhibited the prospect of real-time monitoring applications with high sensitivity, which not only promotes the development of oil quality but also enlarges existing knowledge related to using Raman spectroscopy in chem-/bio-sensing.