Measurements of the sum of inorganic and organic peroxy radicals (RO2) and photolysis rate coefficients J(NO2) and J(O1D) have been made at Cape Grim, Tasmania in the course of a comprehensive experiment which studied photochemistry in the unpolluted marine boundary layer. The SOAPEX (Southern Ocean Atmospheric Photochemistry Experiment) campaign included measurements of ozone, peroxides, nitrogen oxides, water vapor, and many other parameters. The first full length paper concerned with the experiment focuses on the types of relationships observed between peroxy radicals and J(NO2), J(O1D) and O1D)> in different air masses in which ozone is either produced or destroyed by photochemistry. It was found that in baseline air with ozone loss, RO2 was proportional to O1D)>, whereas in more polluted air RO2 was proportional to J(O1D). Simple algorithms were derived to explain these relationships and also to calculate the concentrations of OH radicals in baseline air from the instantaneous RO2 concentrations. The signal to noise ratio of the peroxy radical measurements was up to 10 for 1-min values and much higher than in other previous deployments of the instrument in the northern hemisphere, leading to the confident determination of the relationships between RO2 and J(O1D) in different conditions. The absolute concentration of RO2 determined in these experiments is in some doubt, but this does not affect our conclusions concerned either with the behavior of peroxy radicals with changing light levels or with the concentrations of OH calculated from RO2. The results provide confidence that the level of understanding of the photochemistry of ozone leading to the production of peroxide via recombination of peroxy radicals in clean air environments is well advanced.¿ 1997 American Geophysical Union