Two-dimensional MXenes have attracted great interest because of their metallic conductivity, hydrophilicity, and tunable interlayer structures. but their practical use is limited by restacking, limited processability, and structural instability. Here, a polymer-ligand functionalization strategy is used to engineer MXene surfaces and construct a hierarchical hybrid composite with hollow silica. The polymer ligand suppresses restacking and enables controlled interfacial assembly with hollow silica, yielding a composite with excellent structural stability, enlarged interlayer spacing, and improved dispersion behavior. Consequently, the hybrid composite exhibits enhanced ion transport, cycling stability, and overall electrochemical performance, making it a promising electrode material for sodium-ion batteries. **This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1A6A1A03023788).