Diamondoids are a class of aliphatic molecules with cage-like structures and serve as a bridge between small hydrocarbons and large nanodiamond macromolecules. Because their optical properties are highly dependent on the size, shape, and functionalization of the carbon network, they have many applications in the fields of nanotechnology and spectroscopy. Still, much remains to understand the geometric and electronic effects induced by functionalization of diamondoids. To this end, we perform gas phase photoelectron spectroscopy (PES) of functionalized adamantanes using a helium discharge lamp as a photon source and a hemispherical electron analyzer. We present the photoelectron spectra of 1-cyanoadamantane, 1-amantadine, and 2-adamantanol and compare these to the known PES spectra of adamantane, 1-adamantanol, and urotropine, remeasured herein with improved resolution and a more thorough assignment of vibronic features, with the aid of time-dependent density functional theory calculations.