Freeze-thaw cycle experiments on high performance concrete were carried out while cement was respectively replaced by fly ash for 30%～50%. The test results showed that maximum weight loss rate of concrete was 1.78% and minimum relative dynamic elastic modulus was 94.08% after 300 freeze-thaw cycles for high performance concrete based on low water-cement ratio, efficient air-water-reducing agent and large quantities of industrial waste fly ash. The test data were far less than limits of 5% and 60% in specification. Freeze-thaw resistance performance of high performance concrete with large volume fly ash was excellent according to test results. The high performance concrete with large volume fly ash can meet the requirements of frost resistance performance of concrete in the cold regions. Particularly, it can be fit for the railway concrete engineering.