The interaction between cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulphate (SDS) surfactants with polyethylene oxide (PEO) has been investigated using different techniques such as tensiometry, rheology and scanning electron microscopy (SEM). The driving force responsible for the interaction is supposed to be the minimization of interfacial force between the non-polar polymer parts and the solvent water by association. It is observed that the critical micelle concentration (cmc) increases with the increase in temperature and the cmc of CTAB is smaller as compared to SDS. Viscosity increases with the increase in polymer concentration and is higher in case of anionics. Dense micellar arrangement is seen for cationics. The result shows that the interaction of cationic surfactant is much higher than the anionic surfactant with PEO.