The microstructure is significant for exploring the physical properties of hardened cement paste. In general, the microstructures of hardened cement paste are obtained by microscopy. As a popular method, scanning electron microscopy (SEM) can acquire high-quality 2D images but fails to obtain 3D microstructures.Although several methods, such as microtomography (Micro-CT) and Focused Ion Beam Scanning Electron Microscopy (FIB-SEM), can acquire 3D microstructures, these fail to obtain high-quality 3D images or consume considerable cost. To address these issues, a method based on solid texture synthesis is proposed, synthesizing high-quality 3D microstructural image of hardened cement paste. This method includes 2D backscattered electron (BSE) image acquisition and 3D microstructure synthesis phases. In the approach, the synthesis model is based on solid texture synthesis, capturing microstructure information of the acquired 2D BSE image and generating high-quality 3D microstructures. In experiments, the method is verified on actual 3D Micro-CT images and 2D BSE images. Finally, qualitative experiments demonstrate that the 3D microstructures generated by our method have similar visual characteristics to the given 2D example. Furthermore, quantitative experiments prove that the synthetic 3D results are consistent with the actual instance in terms of porosity, particle size distribution, and grey scale co-occurrence matrix.