An efficient catalyst SO

4

2-

-TiO

2

(ST) from industrial metatitanic acid has been successfully prepared to catalyze hydrolysis of ball-milling cellulose. The results show that the highest catalytic efficiency is obtained for ST calcined at 450℃ (ST-450) with the yield of 21.8% glucose

13.0% 5-HMF and 4.2% furfural at 200℃ for 30 min. The ball milling of cellulose and solid acid catalyst significantly enhances the cellulose hydrolysis. The high Lewis to Brönsted acid sites ratio for ST-450 induced by bidentate ligands between SO

4

2-

and TiO

2

benefits high organics yield

and high total acid sites contribute to the high cellulose conversion. The large pore volume of 0.29 cm

3

·g

-1

and appropriate pore size of 7.35 nm of ST-450 also contribute to the high performance. High reaction temperature over 200℃ exhibits negative effect on glucose and 5-HMF yield due to undesired side reactions

while furfural product is stable in the reaction system. The bidentate ligands between SO

4

2-

and TiO

2

are considered as active acid si

tes for cellulose hydrolysis in water-ethanol solvents.