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In view of the characteristics of erosion environment of underground concrete structure in Guangdong, this paper researched the chloride ion transmission characteristics in concrete under different conditions of water cement ratio, mineral admixtures, and ion concentration and soaking, then analysed the impact on chloride ion transmission speed and comprehensive revealed chloride ion infusibility in concrete in these conditions. Through the analysis of experimental results, the complex mixtures of fly ash and silicon ash is beneficial to the durability of urban underground structure. Especially when the proportion of silicon ash is 5% and fly ash is 30%~40%, which is the most favourable to the improvement of the durability of concrete.