The present disclosure relates to a probe capable of electrochemical and Raman spectroscopic monitoring wherein a Raman-active gold microshell having conductivity is attached to the tip of a glass microcapillary tube in which a conductive material is coated on an inner wall thereof by electroless plating. By coupling the probe with a system capable of moving the probe, the activities of various catalyst materials can be detected quickly and information of intermediate products moving from and adsorbed on the surface can be provided.