Abstract: Single-crystal X-ray diffraction experimentation is a crucial instrumental experiment course in materials science, chemistry, biomedical engineering, and related fields. However, due to limited class hours, it is hard for students to fully master experimental skills under traditional teaching mode. In view of this, we have constructed an online-offline interactive hybrid teaching mode, which encompasses pre-class online theoretical preview and testing, in-class guidance and experimental implementation, and post-class consolidation and extended exercises, aiming to comprehensively enhance students' single-crystal X-ray diffraction experimental skills. Additionally, an innovative digital instructional resource based on the CSD (Cambridge Structural Database) for crystal structure solution and refinement is introduced into the course to address the weakness regarding these aspects. Practical results indicate that, the adoption of the online-offline hybrid teaching mode yield remarkable teaching outcomes, and the students' experimental level and abilities in crystal structure solution and refinement have been significantly improved. This teaching mode and digital instructional resource are highly beneficial for mastering skills in crystal structure solution and refinement, and it is recommended for promotion and application in single-crystal X-ray diffraction experimental teaching.