The invention discloses an N,N,N',N'-dodecyl-tetrasubstituted diphenyl ether sulfonate anionic gemini surfactant and a synthesis method thereof. The structural formula of the anionic gemini surfactantis shown in the description. The anionic gemini surfactant is prepared by a two-step reaction. The synthesis method comprises the following steps: S1, carrying out amine alkylation on 4,4'-diaminodiphenyl ether and bromododecane to obtain N,N,N',N'-dodecyl-tetrasubstituted diphenyl ether; and S2, carrying out a sulfuration reaction on N,N,N',N'-dodecyl-tetrasubstituted diphenyl ether and concentrated sulfuric acid to obtain the target product N,N,N',N'-dodecyl-tetrasubstituted diphenyl ether sulfonate. The surfactant of the invention has a high surface activity, and the synthesis method has the advantages of simplicity, mild reaction conditions, and easiness in separation and purification. The surfactant of the invention is expected to be applied to alkali / surfactant combination flooding,polymer / surfactant binary combination flooding, alkali / surfactant / polymer ternary combination flooding, micro-emulsion emulsifiers in tertiary oil recovery, and also can be compounded with common surfactants to reduce the use cost and create conditions for large-scale application.