A three-dimensional high-order reverse-time migration (3-D HO-RTM) method is proposed to perform subsurface electromagnetic imaging with an ultra-wideband radar (UWBR) system consisting of a multi-input and multi-output antenna array. By using a UWBR system to collect temporal scattering signals, subsurface targets can be detected, and the image of targets can be obtained by imaging methods such as the back-propagation method, frequency-wavenumber migration technique, time-reversal mirror, and reverse-time migration method. The proposed HO-RTM method is based on the high-order finite-difference time-domain (HO-FDTD) method to significantly reduce the computational cost in the conventional RTM method. The measured data from an experimental lunar exploration system Chang'E-5 have been collected on a 7 m × 2.5 m × 2.5 m laboratory model with volcanic ash and validated by the 3-D HO-RTM method. Results show that all buried objects can be effectively identified by the HO-RTM, and its computer memory and CPU time are only 3.87% and 0.7128% of the conventional RTM method, respectively.