The FTIR-ATR technique has been used to obtain structural information for thick polymer samples to which the conventional FTIR method using transmitted infrared radiation could not easily be applied. This technique coupled with polarized radiation has also been used to obtain three-dimensional orientation information for many segments comprising the polymer chain simultaneously. To obtain quantitative orientation values with the FTIR-ATR method, all of the infrared intensity should be normalized with the absorbance of a known reference band, whose absorbance is not affected by any change in structural factors such as the orientation, conformation, and crystallinity. However, this method cannot be applied to polymer samples whose FTIR-ATR spectrum does not include such a reference band. In this work, a new analysis method, called the multiple peak reference (MPR) method, is proposed, which provides a means of obtaining a new reference peak by linearly combining two existing infrared bands. The appropriateness of this new method was tested by comparing the results obtained from the MPR method with the corresponding results from the well-known method (single peak reference (SPR) method) in the case of uniaxially stretched PET and PTT films. A three-dimensional analysis was successfully carried out for a uniaxially stretched PEN film whose three-dimensional orientation information could not be obtained using the polarized FTIR-ATR method, due to the lack of any known single reference peak.