Fly ash is a by-product of coal-fired thermal power plants and offers great potential for the use of resources. To effectively improve the durability of reinforced concrete structures in marine environment and achieve waste to treasure, fly ash is widely used as a pozzolanic material due to its long-hydration characteristics and effects of micro-aggregate, micro-filling and secondary hydration. In this study, both the experimental investigation and numerical simulation are carried out to study the chloride transport characteristics of fly ash cement paste. The variation in chloride diffusivity with fly ash content, water-to-binder ratio and curing age up to 360 days is studied via accelerated conductivity measurement, and it is found that the above three experimental variables have a significant impact on the chloride diffusivity. For the influence of the dosage of fly ash, the optimum dosage is 30%. By introducing specific rules for the particle distribution, the fresh fly ash cement paste is first made. Based on the volume change characteristics of fly ash and cement particles after hydration, the vector hydration model of fly ash cement paste is established by considering the water shortage effect caused by hydration layer interference. After the accuracy of this hydration model is verified by the results from third-party experiments, the random walk algorithm is proposed to calculate the diffusion coefficient of the reconstructed mineral admixture cement paste. By comprehensive comparison with the experimental results from the third-party and self-conducted experiments, the numerical model for predicting the chloride diffusivity of fly ash cement paste is verified.