The invention discloses an auxiliary agent for laser welding, an application thereof and a welding method. The auxiliary agent for laser welding is composed of the following raw materials of, in partsby weight, 35-45 parts of copper oxide, 6-9 parts of aluminum, 19-25 parts of calcium fluoride, and 24-30 parts of calcium carbonate. By means of the auxiliary agent for laser welding, effective welding of an underwater wet-method laser welding technology at the water depth of 8 mm or below can be achieved, meanwhile, defects, namely, internal air holes of welding seams, generated through wet-method welding can be effectively reduced, and the welding seams can be protected. The auxiliary agent for welding is adopted for carrying out underwater wet-method laser welding, the porosity can be greatly reduced, and the porosity can reach 0.5% at the lowest, so that the underwater wet-method welding quality is effectively improved.