Solvent-free and liquid-phase selective oxidation of aromatic alcohols using O2 as an oxidant is a green strategy for the synthesis of aromatic aldehydes and other carbonyl compounds. Wherein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot topic in this process. Herein, a series of manganese oxide-silica (MnSiOx) composites were synthesized using cetyltrimethylammonium bromide as a soft template. During the preparation process, the amounts of tetraethyl orthosilicate and ammonia and the calcination temperature significantly affected the textural properties and Mn cation distributions of MnSiOx. The MnSiOx composites were then employed as catalysts for Pd nanoparticles. In the solvent-free and atmospheric conditions, Pd/MnSiOx materials showed high catalytic conversions of benzyl alcohol (BZA), and the catalytic activity thereof is related to the fractions of Pd0 and Mn3+. As the reaction time and temperature are 4 h and 90 °C, the conversion of BZA (feeding dosage: 4 mL) and the selectivity of benzaldehyde are 64.8 % and 94.9 %, respectively. The catalyst can be reused at least five times without any significant loss of activity. Furthermore, the correlation between physiochemical properties and catalytic activity of Pd/MnSiOx was analyzed.