Yes, you can use Na-EDTA to make TE buffer, and it will work just fine. Typical TE buffer contains: 1 mM EDTA in 10 mM Tris-HCl (pH 8.0).

EDTA is there to chelate divalent cations (like Mg²⁺ and Ca²⁺), which are required by nucleases. This protects your DNA from degradation. You're referring to the disodium salt of EDTA (Na₂EDTA), which is exactly what's commonly used in molecular biology for making TE buffer. Just ensure that you have clean, nuclease-free water, container etc.