In the hydrothermal synthesis of highly ordered mesoporous silica material SBA-15, strong acid is typically required to catalyze the hydrolysis and condensation of silica species. Meanwhile, under strongly acidic conditions, the transition metal ions, e.g., iron ions, are difficult to incorporate into SBA-15 because of the facile dissociation of Fe-O-Si bonds. Here, we demonstrate an acid-free green synthetic strategy for the synthesis of highly ordered mesoporous SBA-15 and Fe-SBA-15 with the assistance of hydroxyl free radicals that are generated by physical or chemical methods. The prepared materials exhibit a large specific surface area compared to the counterparts prepared by conventional method under acidic conditions. Moreover, Fe-SBA-15 shows high metal loading efficiency as over 50%. Density functional theory calculations suggest that the hydroxyl free radicals exhibit higher catalytic activity than H+ ions for the hydrolysis of tetraethyl orthosilicate. This radical-facilitated synthesis approach overcomes the challenge to the direct synthesis of highly ordered SBA-15 and Fe-SBA-15 without adding any acid, providing a facile and environmentally friendly route for future large-scale production of ordered mesoporous materials.