The invention provides a catalytic ozonation system and method and application. The catalytic ozonation system comprises a catalytic ozonation reaction tank (6), a bubble-free high-concentration ozonewater preparation device (5) and a low-energy-consumption refrigerating device (2); high-concentration ozone water (15) enters the catalytic ozonation reaction tank (6) through a jet flow release device (16), fine bubbles are generated, the bubbles are sufficiently mixed with pre-treated waste water (18) to generate an ozonation reaction, and part of organic pollutants in the waste water are removed. The catalytic ozonation reaction tank (6) is filled with a mineral cushion layer (4) and a catalyst (17), the mineral cushion layer (4) and the catalyst (17) act with supersaturated dissolved oxygen and remaining soluble ozone in the high-concentration ozone water respectively to generate hydroxyl radicals, and the organic matter, which is difficult to degrade, in the waste water (18) is decomposed and removed. Compared with a conventional catalytic ozonation technology, the catalytic ozonation system can more efficiently remove the organic pollutants, which are difficult to degrade, in the water.