Spectral CT can separate basis materials, and thus it can provide information on material characterization and quantification. Such information can benefit various clinical applications. However, the presence of non-ideal effects in X-ray imaging systems limits the accuracy of basis images. To achieve high accuracy of material decomposition and high quality of basis images, a novel direct iterative basis material image reconstruction based on maximum a posteriori expectation–maximization algorithm (MAP-EM-DD) is proposed. Furthermore, by incorporating polar coordinate transformation into MAP-EM-DD, MAP-EM-PT-DD is proposed. The iterative formulas of MAP-EM-DD and MAP-EM-PT-DD are derived. To evaluate the proposed methods, a simulated cylinder phantom with inserts that contain polyethylene, hydroxyapatite, salt water, air, and aluminum is established. The methods are quantitatively evaluated for comparative studies. Results show that the proposed methods can remarkably reduce the noise of basis images and error of material decomposition and improve the contrast-to-noise ratios (CNRs) of each material-specific region. Compared with the image domain material decomposition based on FBP algorithm (FBP-IDD), MAP-EM-DD can reduce the noise levels of basis images ranging from 57.4 to 63.6% and the error levels of each material-specific region from 31.7 to 62.1%. Simultaneously, the CNRs of each material-specific region are improved ranging from 63.8 to 237.3%. Compared with MAP-EM-DD, MAP-EM-PT-DD can reduce the noise levels of basis images ranging from 21.4 to 23.6%, the error levels of each material-specific region ranging from 1.9 to 36.3%, and the reconstruction time of basis images by 14.1%. [ABSTRACT FROM AUTHOR]