Some points on how to improve the detection sensitivity of confocal Raman microscopy for the study of surface-enhanced Raman scattering (SERS) of transition-metal electrodes are discussed, including the careful design of the spectroelectrochemical cell, proper selection of the thickness of the solution layer, the binning of charge-coupled device (CCD) pixels, and appropriate setting of the notch filter. Various roughening methods for the Pt, Rh, Fe, Co, and Ni electrode surfaces have been introduced in order to obtain SERS-active surfaces. It has been shown that the appropriate roughening procedure and the optimizing performance of the confocal Raman microscope are the two most important factors to directly generate and observe SERS on net transition-metal electrodes.