The effect of polyethylene glycol (PEG) additive on the synthesis of TS-1 zeolites was investigated by changing the addition amount of PEG and the crystallization time. Adding suitable amount of PEG may effectively inhibit the generation of unfavorable anatase, and result in the formation of TS-1 zeolites enriched tetrahedral framework Ti species with a short crystallization time (1.5 days). The resultant TS-1 zeolites showed significant improvement in catalyzing epoxidation of 1-hexene with H 2 O 2 as oxidant. A turnover frequency (TOF) up to 161 h −1 could be obtained over the anatase-free TS-1 zeolite, much higher than the conventional TS-1 zeolite (TOF: 95 h −1 ). This work demonstrated that using a small amount of PEG additive could be beneficial for the formation of anatase-free TS-1 zeolites, which may have great potential for the catalytic application in H 2 O 2 -mediated olefin epoxidation.