A mild, efficient, and green approach for highly selective synthesis of 1,5-dinitronaphthalene (1,5-DNN) has been devolved from catalytic nitration of 1-nitronaphthalene (1-NN) with NO₂ combined with O₂-Ac₂O over solid superacid S₂O₈²⁻/Fe-ZrO₂. The prepared S₂O₈²⁻/Fe-ZrO₂ catalyst presents better catalytic performance than most of the reported catalysts for this purpose, with 96.8% conversion of 1-NN and 62.6% selectivity of 1,5-DNN under the optimized reaction conditions. The excellent catalytic activity of S₂O₈²⁻/Fe-ZrO₂ can be attributed to its remarkable Lewis acid sites and strong acidity. A possible catalytic nitration reaction pathway of 1-NN with NO₂ over S₂O₈²⁻/Fe-ZrO₂ in the O₂-Ac₂O system was proposed. This work provides a practical strategy for the cost-effective, environmentally friendly, and efficient synthesis of 1,5-DNN with significant industrial application prospects.