The dendritic fibrous silica (KCC-1) was prepared by hydrothermal synthesis, and solid base catalyst K/KCC-1 with different loading was prepared by equal volume impregnation with potassium acetate as precursor. The crystal morphology, pore structure and basic characteristics of K/KCC-1 material were characterized by XRD, FTIR, BET, CO2-TPD and SEM etc. The transesterification performance of dimethyl carbonate (DMC) and ethanol to methyl ethyl carbonate (EMC) was evaluated. The results indicate that the K/KCC-1 catalyst has two types of basic sites, the weak basic sites provided by K-O-Si and the medium strong basic sites provided by K2CO3. With the increase of K loading, the weak basic sites gradually decrease, and the medium strong basic sites gradually increase, enhancing the reaction activity of transesterification. K/KCC-1 with a K loading of no more than 0.9 still maintains the dendritic fiber structure of KCC-1, allowing the reactant molecules to easily diffuse to the Active site. 0.9K/KCC-1 has the highest catalytic activity. Under the optimal reaction conditions of reaction temperature of 80 oC, reaction time of 5 hours, molar ratio of DMC to ethanol of 4:1, and catalyst dosage of 5% of DMC, the conversion rate of DMC is 91.0%, and the EMC selectivity is 95.5%.