To obtain the relation in the electrochemical reduction of $CO_2$ in aqueous $KHCO_3$ colution between an activity for the product and the nature of Cu electrode, the electrode surface was characterized by using two methods: X-ray photoelectron spectroscopy (XPS) and photoelectron emission (PE) measurement. Electrolyses were performed with Cu electrodes pretreated in several ways. The distribution of the products changed drastically with electrolysis time and the pretreatment method. The features in XPS spectra were closely connected with the product distribution. The oxide film at the electrode surface was gradually reduced to bare Cu metal with electrolysis time, resulting in a variation of the product distribution. PE was measured by verying the wavelength of incident light at several temperatures. The dependence of PE on the measurement temperature changed greatly before and after electrolysis.