The fractured surrounding rocks of roadways pose major challenges to safe mining. Grouting has often been used to reinforce the surrounding rocks to mitigate the safety risks associated with fractured rocks. The aim of this study is to develop highly efficient composite ultrafine cement (CUC) grouts to reinforce the roadway in fractured surrounding rocks. The materials used are ultrafine cement (UC), ultrafine fly ash (UF), ultrafine slag (US), and additives (superplasticizer [SUP], aluminate ultrafine expansion agent [AUA], gypsum, and retarder). The fluidity, bleeding, shrinkage, setting time, chemical composition, microstructure, degree of hydration, and mechanical property of grouting materials were evaluated in this study. Also, a suitable and effective CUC grout mixture was used to reinforce the roadway in the fractured surrounding rock. The results have shown that the addition of UF and US reduces the plastic viscosity of CUC, and the best fluidity can be obtained by adding 40% UF and 10% US. Since UC and UF particles are small, the pozzolanic effect of UF promotes the hydration reaction, which is conductive to the stability of CUC grouts. In addition, fine particles of UC, UF, and US can effectively fill the pores, while the volumetric expansion of AUA and gypsum decreases the pores and thus affects the microstructure of the solidified grout. The compressive test results have shown that the addition of specific amounts of UF and US can ameliorate the mechanical properties of CUC grouts. Finally, the CUC22‐8 grout was used to reinforce the No. 20322 belt roadway. The results of numerical simulation and field monitoring have indicated that grouting can efficaciously reinforce the surrounding rock of the roadway. In this research, high‐performance CUC grouts were developed for surrounding rock reinforcement of underground engineering by utilizing UC and some additives.