Low pressure flash thermolysis of different precursor molecules containing-ClO, -ClO3 or -OClO3 yield, when highly diluted in Ne or O2 and subsequent quenching of the products in a matrix at 5 or 15 K, ClOx (x = 1, 3, 4) radicals, respectively. If Ne or O2 gas is directed over solid ClO2 at -120 degrees C and the resulting gas mixtures are immediately deposited as a matrix, a high fraction of (OClO)2 is trapped. This enables recording of IR and UV spectra of weakly bonded (OClO)2 dimers and detailed studying of their photochemistry. For Ne or O2 matrix isolated ClO radicals the vibrational wavenumbers and electronic transitions are only slightly affected compared with the gas phase. In this study strong evidence is found for long lived ClO in the electronically excited 2 [symbol: see text] 1/2 state. A comprehensive IR study of Ne matrix isolated ClO3 (fundamentals at 1081, 905, 567, 476 cm-1) yield i) a reliable force field; ii) a OClO bond angle of alpha e = 113.8 +/- 1 degrees and iii) a ClO bond length of 148.5 +/- 2 pm in agreement with predicted data from quantum chemical calculations. The UV/Vis spectrum of ClO3 isolated in a Ne matrix (lambda max at 32,100 and 23,150 cm-1) agrees well with the photoelectron spectrum of ClO3- and theoretical predictions. The origin of the structured high energy absorption is at 22,696 cm-1 and three fundamentals (794, 498, 280 cm-1) are detected in the C2E state. By photolysis of ClO3 with visible light the complex ClO.O2 with ClO in the 2 [symbol: see text] 1/2 state is formed. In an extended spectroscopic study of the elusive ClO4 radical, isolated in a Ne or O2 matrix, three additional IR bands, a complete UV spectrum and a strong interaction with O2 are found. This leads to the conclusion that ClO4 exhibits C2v or Cs symmetry with a shallow potential minimum and forms with O2 the previously unknown peroxy radical O3ClO-O2. All these results are discussed in the context of recent developments in the chemistry and spectroscopy of the important and interesting ClOx (x = 1-4) family of radicals.