Weakly acidic Zr‐SBA‐15 materials were synthesized by using a novel method to maximize the accessibility of zirconium sites in view of their catalytic applications. Synthesized materials at different ageing temperatures were characterized by means of several techniques such as XRD, N2 physisorption, TEM, ammonia temperature‐programmed desorption, and X‐ray photoelectron spectroscopy and subsequently used in a test acid‐catalyzed process such as the microwave‐assisted alkylation of anisole with benzyl chloride. Reaction results revealed the very high catalytic activity of the prepared Zr‐SBA‐15 materials, which depended mostly on the accessibility of the supported zirconium species and their speciation.