The explosion characteristics of chlorine dioxide gas have been studied for the first time in a cylindrical exploder with a shell capacity of 20 L. The experimental results have indicated that the lower concentration limit for the explosive decomposition of chlorine dioxide gas is 9.5% ([ClO(2)]/[air]), whereas there is no corresponding upper concentration limit. Under the experimental conditions, and within the explosion limits, the pressure of explosion increases with increasing concentration of chlorine dioxide gas; the maximum pressure of explosion relative to the initial pressure was measured as 0.024 MPa at 10% ClO(2) and 0.641 MPa at 90% ClO(2). The induction time (the time from the moment of sparking to explosion) has also been found to depend on the concentration of chlorine dioxide gas; thus, at 10% ClO(2) the induction time was 2195 ms, but at 90% ClO(2) the induction time was just 8 ms. The explosion reaction mechanism of ClO(2) is of a degenerate chain-branching type involving the formation of a stable intermediate (Cl(2)O(3)), from which the chain-branching occurs. Chain initiation takes place at the point of ignition and termination takes place at the inner walls of the exploder.