The photoionization efficiency (PIE) spectrum of Cl 2 O was measured over the wavelength range λ ) 98-117 nm by using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. A value of 10.90 9 ( 0.01 6 eV was obtained for the adiabatic ionization energy (IE) of Cl 2 O from analysis of the photoionization thresholds. The ClO radical was produced Via the reaction F + Cl 2 O f FCl + ClO and the PIE spectrum of ClO was measured over the wavelength range λ ) 105-117 nm. Analysis of the photoionization threshold yields a value of IE of ClO(X 2 Π 3/2 ) ) 10.88 5 ( 0.01 6 eV. The appearance energy (AE) of ClO + (from the dissociative ionization of Cl 2 O) was determined from the PIE spectrum of ClO + over the wavelength range λ ) 98-104 nm. Combining the AE 298 value, 12.29 6 ( 0.03 2 eV, with known thermodynamic quantities yields a value for ∆ f H°2 98 (Cl 2 O) ) 77.2 ( 3.4 kJ mol -1 . From the value for ∆ f H°2 98 (Cl 2 O) and the equilibrium constant for the reaction Cl 2 O + H 2 O T 2HOCl, a value for ∆ f H°2 98 -(HOCl) ) -76.8 ( 3.5 kJ mol -1 is obtained. These results for IE(Cl 2 O), IE(ClO), AE 298 (ClO + , Cl 2 O), ∆ f H°2 98 -(Cl 2 O), and ∆ f H°2 98 (HOCl) are compared with previous estimates or measurements.