The problems rendered from the conventional time marching, referring to stepwise time marching scheme (STMS) adopted in boundary element method (BEM) for chloride diffusion in concrete structures, were investigated, and a new time marching, referring to initial time marching scheme (ITMS) in BEM, was developed for evaluation of service life of the concrete structures under chloride environment. Results of the numerical examples show that the ITMS-BEM proposed can eliminate domain integral and simplify the computational model, so that the stability in iteration process can be improved, resulting in better efficiency and accuracy, compared with the STMS-BEM. It can also be concluded that the dimensions of the diffusion of chloride can affect the service life of the concrete structure significantly, which should be taken into account in structural design.