A transition-metal-free synthetic approach for constructing alkylated aryl tetrazoles has been developed using n-Bu4NI as the catalyst and t-BuOOH as the oxidant. It involves the direct C鈥揘 bond formation through sp3 C鈥揌 activation. A wide range of benzylic C鈥揌 substrates (or alkyl ethers) and aryl tetrazoles undergo this reaction smoothly to deliver the corresponding products in good yields.