The strain effect on La0.67Ca0.33MnO3 and La0.8Ba0.2MnO3 thin films on SrTiO3 (001) substrate with different thicknesses has been studied by X-ray absorption near edge spectroscopy (XANES), which can reveal the details of the coupling between cations and anions. The strain may suppress the TC of LCMO films while enhancing that of LBMO films. The theoretical calculation results suggest the unoccupied states of the third structure of XANES are formed by much more complex hybridization of O 2p to Mn 4sp, La 6s and (Ca 4sp or Ba 6sp) orbitals. The change of the absorption intensity of the second and third structures is compatible to the TC change of both films due to the strain effect. This strongly suggests that the strain effect on LCMO and LBMO thin films is mainly associated with the bonding situation between O and La(Ca or Ba) ions.