Dichlorocarbene (CCl2), generated by laser flash photolysis of dichlorodiazirine, formed pi- and O-ylidic complexes with aromatic ethers such as anisole, 1,3-dimethoxybenzene, 1,3,5-trimethoxybenzene, dibenzofuran, and dibenzo-18-crown-6 and with the aromatic ester phenylacetate. These complexes were visualized by UV-vis spectroscopy, and they retarded the addition of CCl2 to tetramethylethylene by factors of 18-152. Computational studies based on density functional theory provided structures and energetics for the transient species and rationalized their absorption spectra. Complexes were not observed between CCl2 and simple, nonaromatic ethers Such as THF, dioxane, or 18-crown-6, nor did these ethers much affect the addition rate of CCl2 to tetramethylethylene. Computations also suggested that pi-complexes of CCl2 and, e.g., mesitylene and durene, were energetically reasonable transients. Although these species were not detected spectroscopically, the aromatic compounds did slow the addition of CCl2 to tetramethylethylene by factors of 15 and 31, respectively.