Oxygen reduction reaction (ORR) on Pt microelectrode was used for developing a micro pH sensor for scanning electrochemical microscopy (SECM) study in this work. When the potential of Pt microelectrode was held constant in ORR region, the ORR current (cathodic current) increased with decreasing solution pH and vice versa. The response time of the ORR current to pH changes was measured to be ca. 30ms which implies that the pH response is fast enough for monitoring the temporal pH changes. Furthermore, a fine linear relationship was found to exist between the half wave potential of ORR (E 1/2) and the solution pH value, and the slope is −46mV/pH. The Pt micro pH sensor was located 1μm above the LaNi5−x Al x (x =0, 0.3) substrate electrode surface in pH=9 KOH solution to perform the tip–substrate voltammetry of SECM. In tip voltammogram, the ORR tip current qualitatively reflects the transit solution pH changes during LaNi5−x Al x discharge reaction. Also, the minimum values of the solution pH near LaNi5 and LaNi4.7Al0.3 surface during the discharge reaction were quantitatively detected; they were 7.17 and 7.57, respectively. The result indicates that Al partial substitution for Ni degrades the maximum discharge ability of the alloy and decreases the hydrogen diffusion coefficient in alloy bulk.