AbstractA mesoporous Mn1Zr0.5Oy solid solution is prepared with a template‐free co‐precipitation method and is used as an efficient heterogeneous catalyst for oxidative coupling of benzyl alcohol and aniline in the absence of base under mild conditions. XRD, XPS, N2 physisorption, H2‐TPR, O2‐TPD, NH3‐TPD and CO2‐TPD were used to study the influence of calcination temperature on the structure, redox properties, acidity‐basicity, as well as the catalytic behaviors of the Mn1Zr0.5Oy catalyst. The results show that the optimal catalyst calcined at 400 °C displays the highest specific surface area (228 m2 g−1), highest fraction of unsaturated Mn3+ ions (45.4 %) and reactive Osurf. species (52.5 %), and the highest acidity (1.06 mmol g−1) and basicity (0.48 mmol g−1). Thereby, an enhanced benzylideneaniline formation (5.50 mmol gcat−1 h−1) based on a 99 % yield is obtained at 80 °C under air atmosphere. This is one of the top results ever reported for all the Mn‐based catalysts. The structure‐activity relation is finally discussed.