We have developed a combined Surface-enhanced raman spectroscopy (SERS) and mechanically controllable break junction (MCBJ) method to detect and characterize molecular junctions formed by two electrochemically nanofabricated electrodes on silicon chips. The method allows us to obtain vibrational spectra of the molecular junction and perform electron transport measurement on the molecules simultaneously. The preliminary I/V characterization and SERS measurement on an asymmetric molecule, OPE-NO

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... , and a symmetric molecule, OPE, were conducted. This approach may provide new insights into not only electron transport in molecules, but also the enhancement mechanism in single-molecule SERS.