Amphiphilic poly(ionic liquids), PILs, derived from natural products attracted great attention as a green chemical in the field of the surface chemistry and petroleum industry. In the present work, new surface active PILs were synthesized from cardanol cashew nut oil as a hydrophobic alkyl phenol. The phenol group was etherified with diethanolamine, ethanolamine, and tetraethylene glycol using linking agent based on beta,beta-dicholorodiethyl ether to insert nonionic hydrophilic groups into cardanol. The amine group was quaternized with 2-acrylamido-2-methyl-1-propanesulfonic acid to produce polymerizable ionic liquids that polymerized to obtain new PILs. The chemical structure of the prepared new PILs was elucidated from (HNMR)-H-1 and elemental analysis. The surface activity of the prepared PILs was determined from the surface and interfacial tension measurements of their aqueous solution. The ability of the prepared PILs to disperse the asphaltene fractions of the heavy Arabian crude oil was studied. It was used to explain their demulsification performance and efficiency data when they were used as demulsifiers for crude oil water emulsions. The demulsification data elucidate that the PILs have greater ability to reduce IFT and can separate water effectively. Moreover, the PILs have a greater tendency to disperse asphaltene and perform better as demulsifier than that flocculate asphaltenes.