In the treatment of goafs in traffic engineering, technical problems such as those related to large-volume grouting and the precise control of material properties are often encountered. To address these issues, we developed a new composite material comprising cement-fly ash-modified sodium silicate (C-FA-MS). The setting time, fluidity, unconfined compressive strength, and microstructure were varied for different proportions of cement-sodium silicate (C-S) slurry, cement-fly ash-sodium silicate (C-FA-S) slurry, and C-FA-MS slurry, and their performances were compared and analysed. The experimental results showed that the initial setting time of the slurry was the shortest when both the original sodium silicate volume ratio (
V
S
) and modified sodium silicate volume ratio (
V
MS
) were 0.2. The final setting time of the C-S and C-FA-S slurries tended to decrease but then increased with decrease in
V
S
, while that of the C-FA-MS slurry increased with lower
V
MS
. The fluidity of the C-FA-S and C-FA-MS slurries decreased with decrease in
V
S
or
V
MS
at different fly ash admixture ratios. The consolidation compressive strength of C-S increased with decreasing
V
S
, while that of C-FA-S showed a considerable increase only when
V
S
decreased from 0.4 to 0.2. Meanwhile, the compressive strength of the C-FA-MS concretions first increased and then decreased with decrease in
V
MS
. Microstructural analysis revealed that there were more cracks in the C-S agglomerate, the fly ash in the C-FA-S agglomerate reduced the relative density of the skeletal structure, and the stronger cross-linking in the C-FA-MS agglomerate improved the strength of the agglomerate. Under the condition of unit grouting volume, the cost of the C-FA-MS slurry was approximately 44.7% and 31.3% lower than that of the C-S and C-FA-S slurries, respectively. The new C-FA-MS material was applied for the treatment of the goaf in the Wu Sizhuang coal mine. Core drilling detection and audiofrequency magnetotelluric survey revealed that the goaf was sufficiently filled.