The invention discloses a composite metal photocatalysis system which is represented by Ni-M-X-Y-Z, wherein M is selected from the group consisting of Al, Ag, Bi, Cd, Ge, Sb and Sn; x is selected fromthe group consisting of triphenylphosphine, triethylphosphine, tributylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine; Y is selected from the group consisting of carbon nanorods, molecular sieves, ordered mesoporous carbon and silicon dioxide; Z is selected from the group consisting of diphenyl disulfide, dicumyl peroxide, hydrazine and 2,4-dinitrophenylhydrazine; the mass fractionof Ni is 10-20%; the mass fraction of M is 20-30%; the mass fraction of X is 20-40%; the mass fraction of Y is 15-40%,; and the mass fraction of Z is 10-30%. The catalytic system is used for preparing 1,1,2,3,3-pentamethylindane through free radical cycloaddition of alpha-methylstyrene and 2-methyl-2-butene, an conversion rate is larger than 90%, and selectivity is larger than 85%; and a catalystis stable and not prone to loss in the free radical cycloaddition reaction. A method provided by the invention is easy to operate and good in economic benefit.