The present invention discloses a N,N,N′,N′-tetradodecyl-substituted diphenyl ether sulfonate anionic Gemini surfactant and the synthesis method thereof. It has a structural formula of: and is prepared in a two-step reaction comprising: S1. subjecting 4,4′-diaminodiphenyl ether and bromododecane to an amine alkylation reaction to obtain N,N,N′,N′-tetradodecyl-substituted diphenyl ether; and S2. sulfonating the N,N,N′,N′-tetradodecyl-substituted diphenyl ether with concentrated sulfuric acid to produce the target product, N,N,N′,N′-tetradodecyl-substituted diphenyl ether sulfonate. The surfactant of the present invention has a high surface activity and can be synthesized with a simple procedure under mild reaction conditions, and can be easily separated and purified. The surfactant of the present invention is promising in applications for alkaline/surfactant in tertiary oil recovery, for polymer/surfactant binary compound flooding, alkaline/surfactant/polymer tertiary compound flooding, microemulsion emulsifier, and the like, and may also be compounded with common surfactants to lower the cost, thereby enabling its application in a large scale.