As rechargeable metal-air batteries will be ideal energy storage devices in the future, an active cathode electrocatalyst is required with bi-functionality on both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during discharge and charge, respectively. Here, a class of perovskite cathode catalyst with a micro-tubular structure has been developed by controlling bi-functionality from different Ru and Ni dopant ratios. A micro-tubular structure is achieved by the activated carbon fiber (ACF) templating method, which provides uniform size and shape. At the perovskite formula of LaCrO3, the dual dopant system is successfully synthesized with a perfect incorporation into the single perovskite structure. The chemical oxidation states for each Ni and Ru also confirm the partial substitution to Bsite of Cr without any changes in the major perovskite structure. From the electrochemical measurements, the microtubular feature reveals much more efficient catalytic activity on ORR and OER, comparing to the grain catalyst with same perovskite composition. By changing the Ru and Ni ratio, the LaCr0.8Ru0.1Ni0.1O3 micro-tubular catalyst exhibits great bi-functionality, especially on ORR, with low metal loading, which is comparable to the commercial catalyst of Pt and Ir. This advanced catalytic property on the micro-tubular structure and Ru/Ni synergy effect at the perovskite material may provide a new direction for the next-generation cathode catalyst in metal-air battery system.