To achieve high-performance Sb-based anodes for Na-ion battery (NIB), various approaches for obtaining amorphous C-containing Sb composite (Sb@C), Sb-based intermetallic compounds (TiSb₂ and NbSb₂), and Na-inactive metal carbide and amorphous C-containing Sb composites (Sb@TiC@C and Sb@NbC@C) have been introduced. First, Sb@C was prepared using a simple solid-state ball-milling, and then its potential as a NIB anode material was investigated. The electrochemical phase change mechanism of Sb during the sodiation/desodiation of Sb@C was investigated using various ex situ analytical techniques. Sb was found to sequentially transform into NaSb and Na₃Sb during sodiation and NaSb and Sb during desodiation. Second, as another trial to further improve the electrochemical performance of Sb, Sb-based intermetallic compounds of TiSb₂ and NbSb₂ were synthesized by alloying reaction via a simple solid state heat-treatment and their potential as NIB anode materials was investigated. Lastly, the Sb@TiC@C and Sb@NbC@C nanocomposites comprising tiny (~3–5 nm) Sb nanocrystallites and Na-inactive metal carbide (TiC/NbC) matrix embedded in buffering amorphous C were synthesized by alloying and dealloying reaction. The Sb@TiC@C and Sb@NbC@C demonstrated highly reversible, stable capacity (Sb@TiC@C: 746 mAh cm⁻³, Sb/NbC/C: 726 mAh cm⁻³ after 100 cycles) and fast rate capability with exceptional capacity retentions after 400 cycles (Sb@TiC@C: ~710 mAh cm⁻³ at 2 C rate, Sb@NbC@C: ~680 mAh cm⁻³ at 2 C rate). Therefore, the Sb-based nanocomposites synthesized by alloying and dealloying are considered to be possible new anode materials for use in high-performance NIBs.