Abstract The HO2 radical is one of the most important intermediate species in atmospheric chemistry. We report on the development of a new photoreactor with first in-situ measurement of HO2 radical photostationary concentrations using continuous wave cavity ring-down spectrometry (cw-CRDS). Characterization of the actinic photon flux was carried out by NO2 actinometry. Photolysis of Cl2/methanol mixtures in air under UV light allowed the measurement of HO2 photostationary concentrations of a few 1010 molecules cm-3 with an HO2 detection limit of 1.5 × 1010 molecules cm-3 at 6638.207 cm-1. The feasibility of HO2 direct measurement in a reaction chamber is demonstrated through the measurement of the HO2 overall loss at different pressures showing the importance of HO2 diffusion and wall loss in such low pressure quartz reactor. The rate coefficient for the HO2+HO2 reaction has been measured at 6.6, 24 and 118 mbar and found to be in good agreement with the recommended value.