Understanding the effects of synthetic parameters in the catalytic activity of heterogeneous catalysts is of utmost importance when aiming for optimal reaction conditions. Hence, we disclose in this work the synthesis and characterization of cerium-modified MCM-41 materials. In addition, it was observed for the first time, differences in catalytic activity when using different cerium synthetic precursors: CeCl₃·7H₂O and Ce(NO₃)₃·6H₂O (Ce-MCM-Cl and Ce-MCM-NO₃, respectively). A mechanism for cerium incorporation in MCM-41 was proposed, where [Ce(OH)₃] species were hydrogen bonded to silicate anions, forming framework Ce-O-Si bonds during condensation and, consequently, causing distortion of the typical hexagonal mesophase. It was also observed that Ce(OH)₃ formed aggregated layers with template assemblies during synthesis, resulting in non-framework CeO₂ species on the MCM-41 surface after calcination. These CeO₂ species were preferentially formed for Ce-MCM-NO₃ and were attributed to the nitrate ions’ strong binding to template molecules. In the solvent free liquid-phase oxidation of benzyl alcohol (BzOH), Ce-MCM-Cl achieved better BzOH conversions and benzaldehyde (BzD) yields, while Ce-MCM-NO₃ offered increased BzD selectivity. The catalysts’ reusability was also studied over three catalytic runs, where Ce-MCM-NO₃ was more resistant than Ce-MCM-Cl towards deactivation. The observed catalytic behavior shows the importance of metal precursors in the obtainment of materials with desirable final properties.