The invention relates to a complex catalyst for viscosity reduction of thick oil by hydrothermal catalytic cracking and application thereof. The complex catalyst is prepared by the following steps of: 1) selecting raw materials: selecting 2 to 3 mass parts of C12-C18 aliphatic carboxylic acid, 1 to 2 mass parts of ethylene dimine, 3 to 5 mass parts of sodium fluoroacetate, 1 to 2 mass parts of sodium hydroxide, 3 to 5 mass parts of nickel chloride hydrate and 140 to 180 mass parts of toluene; and 2) mixing the C12-C18 carboxylic acid and ethylene dimine, then heating to 160 to 180 DEG C in anoil bath and reacting for 2 to 3 hours, cooling to 90 to 95 DEG C, adding sodium chloroacetate-containing aqueous solution, stirring, reacting for 40 to 50 minutes and then adding NaOH, continuously reacting for 10 to 13 hours at the temperature of between 90 and 100 DEG C, finally adding the NiCl2.6H2O and the toluene, refluxing and splitting water for 3 to 5 hours and filtering, and performing reduced pressure desolvation on the filtrate to obtain the catalyst, wherein after the reaction is finished, the viscosity reduction rate of the thick oil reaches over 90 percent, and 9 to 15 percent of heavy component is cracked into a light component.