This study aimed to produce high-performance dissolving pulps from corn stalks using a combination of cold caustic extraction (CCE) and deep eutectic solvent (DES) method. Results showed that CCE not only removed hemicelluloses but also altered the structure of cellulose, increasing its polymerization degree and influencing the Fock reactivity of the dissolving pulp (reduced to 10.55%). Subsequent treatment with DES effectively dissolving the remaining hemicelluloses while disrupting the cellulose crystallinity and improving the Fock reactivity of the dissolving pulp (increased to 72.14% from 10.55%). The study implied that the hydrogen bond donor in DES played a crucial role in breaking the cellulose chains and improving the reactivity of the dissolving pulp. The dissolving pulp produced from corn stalks using through the combination of CCE and DES method exhibited the cellulose content of 94.46% and the Fock reactivity of 72.14%, providing a new strategy for the high-value utilization of stover resources.