Probability distribution law of corrosion initiation time of steel in concrete under chloride environment is discussed. Based on the Fick’s second law, by Monte Carlo, frequency distribution, distribution type and probability density is analyzed. The statistic parameters of the factors influencing the probability distribution of corrosion initiation time are studied and the expression for sensitivity analysis of corrosion initiation time is deduced. By sensitivity analysis can know, corrosion initiation time is found to be more sensitive to cover than the diffusion coefficient, and more sensitive to surface chloride concentration than the critical chloride level. The analysis of the paper perfects the methods of predicting the corrosion initiation time.