Modulating the A-site deficiency is a useful method to achieve the exsolution of nanoparticles on the surface of perovskite, improving the catalytic activity. However, rules for designing the deficiency value and its roles on the structure and performance remain unclear. In this study, a wide range of A-site deficiencies of (La0.4Sr0.6)1-αTi0.95Ni0.05O3±δ (LSTN, α = 0.00, 0.13, 0.15, and 0.18) titanate perovskite materials was designed to systematically investigate their crystal structure, binding energy, oxygen vacancy concentration, exsolution process, and electrochemical performance. An extremely high conductivity (e.g., 331.75 S cm-1@800 °C, 5% H2/Ar) was obtained in parallel with enhanced catalytical activity in SOFC and SOEC modes. The A-site-deficient samples displayed a higher conductivity, oxygen vacancy concentration, and power output than the stoichiometric samples (α = 0.00). The best maximum power density of 78.74 mW cm-2 and the highest population density of 25 particles per μm2 were obtained on the deficient LSTN with α = 0.13. These findings suggest that LSTN is an exceptionally promising material for solid oxide cell (SOC) electrodes.