Despite the vast body of literature dedicated to understanding metallic nanoparticles, little is known about how the organic ligands affect the electronic band structure in gold nanoparticles. Herein, we report an effective and inexpensive method of probing the electronic band structure of gold nanoparticles using NMR spectroscopy, and then use this technique to demonstrate that manipulation of the ligand shell composition is a robust and underutilized method for the tunability of these structures.