Polymeric surfactant can simultaneously thicken aquous phase and reduce water–oil interfacial tension(IFT), which makes it present a great application prospect in the oilfield taword enhanced oil recovery(EOR). There are two kinds of polymeric surfactant with different molecular structures are commonlyused to realize the salt resistance, thermal endurance and shear resistance. However, the influence ofthe molecular structure of polymeric surfactant on their properties related on EOR are not well understood. In the work, we synthesized two kinds of polymeric surfactants with different molecular structurewhich respectively named intermolecular association molecule (IAM) and rigid chain molecule (RCM). Their physico-chemical properties, porous media transportation and EOR are compared with a series ofexperiments. It is found that the hydrodynamic characteristic sizes and retention of IAM are higher thanthose of RCM via the membrane filtration test and nuclear magnetic resonance (NMR) scan. These featuresmake IAM have a larger resistance factor and residual resistance factor than RCM and hydrolyzedpolyacrylamide (HPAM) in the same viscosity. Compare to HPAM with shear thinning, RCM presents aNewtonian fluid region and IAM presents a shear thickening region when the shear rate is lower than1 s 1. The spatial structure of IAM can pack oil drop into its network, which make it easy to form oilin-water-in-oil (O/W/O) emulsions. Moreover, the concentration and water–oil ratio (WOR) rarely affectthe stability of IAM emulsions once the intermolecular association generated. The increamental oil recoveryfactor of IAM is 17.5% after water flooding in the three-layer core flooding experiments with the permeabilityof 500 mD, 1500 mD and 3000 mD at 55℃, which is higher than that of 14.5% for RCM and11.4% for HPAM.