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During the electrolysis of water in an acidified medium, ozone is produced, in association with oxygen, at the anode. This ozone is found to be depleted in heavy isotopes ([sup.18]O and [sup.17]O), with respect to the source water, following a strict mass-dependent rule. Our experiments also suggest that the isotopes are distributed at the apex and base positions of the bent ozone molecule in a random fashion, without obeying the zero-point energy constraint Endowed with these characteristics, the electrolytic ozone provides a source of reference that has a known internal heavy isotope distribution for spectroscopic studies. In addition, this ozone, when subjected to photolytic decomposition, can be used as a source of atomic oxygen with mass-dependent isotope ratios that can be varied by simply changing the water composition. Such an oxygen source is important for studying isotope effects in gas-phase recombination/exchange reactions such as COO + [O.sup.*] [right arrow] [[COOO.sup.*]] [right arrow] [COO.sup.*] + O.