Observation images from hyperspectral (HS) sensors on satellites and aircraft can be used to map minerals in greater detail than those from multispectral (MS) sensors. However, the coverage of HS images is much less than that of MS images, so there are often cases where MS images cover the entire area of interest while HS images cover only a part of it. In this study, we propose a new method to more reasonably expand the mineral map of an HS image with an MS image in such cases. The method uses various mineral indices from the MS image and MS sensor’s band values as the input and HS image-based mineral classes as the output. Random forest (RF) two-class classification is then applied iteratively to determine the distribution of each mineral in turn, starting with the minerals that are most consistent with the HS image-based mineral map. The method also involves the correction of misalignment between HS and MS images and the selection of input variables by RF multiclass classification. The method was evaluated in comparison with other methods in the Cuprite area, Nevada, using the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) and Hyperspectral Imager Suite (HISUI) as HS sensors and the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) as MS sensors. As a result, all of the evaluated region-expansion methods with an HS–MS image pair, including the proposed method, showed better performance than the method using only an MS image. The proposed method had the highest performance, and the inter-mineral averages of the F1-scores for the overlap and non-overlap areas were 85.98% and 46.46% for the AVIRIS–ASTER image pair and 82.78% and 42.60% for the HISUI–ASTER image pair, respectively. Although the performance in the non-overlap region was lower than in the overlap region, the method showed high precision and high accuracy for almost all minerals, including minerals with only a few pixels. Misalignment between the HS–MS images is a factor that degrades accuracy and requires precise alignment, but the misalignment correction in the proposed method could suppress the effect of misalignment. Validation studies using different regions and different sensors will be carried out in the future.