Polarimetric decomposition is an effective way to analyze the scattering mechanism of targets in polarimetric synthetic aperture radar (PolSAR) images. However, the analysis of urban areas is frequently a challenge. Most decomposition methods use a rotated dihedral derived via rotation matrix to model the double-bounce scattering mechanism of buildings. However, according to electromagnetic theory, the existing dihedral model is not accurate, especially when the orientation angle of the dihedral is large. Therefore, the double-bounce scattering contribution in urban areas with large orientation angles will be difficult to extract. To address this problem, based on physical optics (PO) and geometric optics (GO), the interaction process of electromagnetic waves and the rotational dihedral is analyzed, and then a modified rotational dihedral model (MRDM) is proposed for the accurate representation of the rotational double-bounce scattering mechanism. Accordingly, MRDM is introduced to a five-component decomposition method (MRDM-5SD) to analyze the scattering components in an urban area. The validity of MRDM-5SD is demonstrated using several data sets. The experimental results show that the power contributions of double-bounce scattering in urban areas with large orientation angles increase by using MRDM-5SD. Therefore, MRDM can provide support for feature extraction and target detection in urban areas.