The invention discloses an environment-friendly fuel oil composite emulsifier. The composite emulsifier comprises a basic component and a modified component with the mass ratio being (4-6):1, whereinthe basic component comprises 40 to 60 parts of acrylic monomers, 2 to 10 parts of perfluorooctane sulfonate, 2 to 4 parts of benzyl butyl Phthalate, 0.5 to 2 parts of nonylphenol polyoxyethylene ether, and 6 to 10 parts of methylbenzotriazole; the modified component comprises 6 to 10 parts of sulfomethyl sodium humate, 10 to 20 parts of Span 80, 10 to 30 parts of cobalt naphthenate, 5 to 10 partsof triisopropanolamine, 18 to 25 parts of phthalic anhydride, 10 to 15 parts of glyceryl oleate, 4 to 8 parts of octadecanoic acid. The composite emulsifier can be applied to various oil product systems, and is wide in application, simple to manufacture, low in cost and good in stability.