The invention discloses an auxiliary chemical processing and scanning method for thermal barrier coating discharge at an outlet of an air film cooling hole. The method comprises the steps that according to the shape and size requirement of the compound angle outlet of the air film cooling hole, model design and parameter setting are carried out for the orifice of the air film cooling hole, according to the model deign and processing and scanning parameter setting of the orifice of the air film cooling hole, the scanning track is planned, and a processing numerical control code is generated; and scanning is carried out according to the processing numerical control code. The method has the following beneficial effects that by the adoption of the auxiliary chemical processing and scanning technology for ceramic thermal barrier coating discharge, the technology is compatible with a pulse power supply integrating electrical discharge machining and electrolytic machining and a working solution circulating system, and the combined technology switched fast with base body high-temperature alloy electric machining can be achieved.