Highly ordered gold NC/silica films are synthesized by self-assembly of water-soluble gold nanocrystal micelles and soluble silica using a sol-gel spin-coating technique. The optical properties are analyzed using ellipsometry and ultraviolet-visible spectroscopy. The absorption spectra show a strong surface plasmon absorption band at ∼520 nm for all samples. Angular excitation spectra of the surface plasmon show a steep dip in the reflectivity curve at ∼65°. Charge transport behavior of the films is examined using metal-oxide-semiconductor (MOS) structures.MOS capacitor samples exhibit charge storage with discharge behavior dominated by electron transport within the gold NC arrays.