Abstract 2,6-Methylacylnaphthalene is an important organic chemical raw material, mainly used as a precursor for synthesizing polyethylene 2,6-naphthalene dicarboxylate (PEN). The heterogeneous catalyst molecular sieve catalyzes the acylation of 2-methylnaphthalene to synthesize β,β-methylacylnaphthalene, which has good activity, is green and environmentally friendly, with simple post-treatment. Different molecular sieves and reaction solvents were selected, and Hβ molecular sieves were more suitable for the acylation reaction of 2-methylnaphthalene. The reaction results were better when sulfolane was used as a solvent in this paper. The catalytic performances of citric acid-modified Hβ molecular sieve (SiO2/Al2O3 of 25) and unmodified molecular sieve were investigated and compared. The results showed that modification with low-concentration citric acid increased the amount of mediate strong acid and Bronsted acid, the specific surface area, pore volume, and pore size of Hβ zeolite. When the concentration of citric acid was 0.3 mol·L−1, the modification time was 48 h and the calcination at 550°C for 3 h had the best catalytic activity. By further optimizing the acylation process, the conversion rate of 2-methylnaphthalene increased to 88.82%, and the yield of β,β-methyl propyl naphthalene increased to 82.12%.