The invention discloses a demulsifier rich in various functional groups, and a preparation method thereof. The demulsifier comprises the following components in parts by weight: 15 to 40 parts of hydrogen-containing silicon oil, 10 to 40 parts of allyl polyether, 10 to 35 parts of acrylic acid, 15 to 30 parts of acrylic ester, 0.5 to 4 parts of a catalyst, 0.5 to 6 parts of an initiator, 1 to 2 parts of a chain transfer agent, 1 to 2 parts of a chain terminating agent, 3 to 5 parts of a surfactant, 1 to 2 parts of an accelerant and 10 to 25 parts of deionized water. The demulsifier is single component, HLB can be adjusted by the synthetic raw materials, high amphipathy is achieved, ether bond, ester bond and carboxylate radical exist in the molecular structure of the prepared demulsifier at the same time, silicon various functional groups are introduced, and the demulsifier can act on crude oil emulsion well. The obtained demulsifier has the characteristics of small use amount, good dehydration effect, low demulsification temperature, clean dehydrated water quality, wide use range and the like.