A magnetic nano-solid acid catalyst Fe3O4-PDA-SO3H was synthetized through an efficient method, as an eco-friendly and more efficient catalyst. The obtained catalyst has uniform core-shell structure, appropriate particle size, and high acid density. Fe3O4-PDA-SO3H was applied to catalyze the esterification of levulinic acid (LA) with alcohols of different chain length to produce the levulinate esters. The catalytic effect was optimized from the aspects of catalyst dosage, reaction temperature, and acid-alcohol molar ratio. Furthermore, the response surface optimization method was used to obtain the optimal conditions. Verified under these conditions, the experimental results showed that the conversion rate of LA can reach 95.87%, which was much higher than common cationic exchange resin Amberlyst 36 and Amberlyst 46. Furthermore, the recovery and reuse of the Fe3O4-PDA-SO3H was demonstrated six times without obvious loss in the activity.