p-Nitrophenylchlorocarbene (PNPCC) reacted reversibly with tetrahydrofuran (THF), tetrahydropyran (THP), 1,3-dioxane (1,3-D), and 1,4-dioxane (1,4-D) to form O-ylides 8, 9, 10, and 11, respectively. The O-ylides were visualized by their characteristic UV-vis spectroscopic signatures. Equilibrium constants (K) were determined spectroscopically, and studies of K as a function of pentane/1,2-dichloroethane (DCE) solvent blends illustrated the dependence of K on solvent polarity. Electronic structure calculations based on density functional theory provided carbene/ether O-ylide structures and energetics, as well as electronic spectroscopic parameters for use in the determination of K. Comparisons of the computed and experimental data were generally satisfactory.