Experiments have been carried out to study the influence of moisture condition, including moisture content and its distribution, on the chloride diffusion in partially saturated ordinary Portland cement mortar. The mortar samples with water-to-cement (w/c) ratios of 0.4, 0.5 and 0.6, cured for 1 year, were preconditioned to uniform water saturations ranging from 18 to 100%. The interior relative humidities of these partially saturated cement mortars, i.e. water vapour desorption isotherm (WVDI), were measured. The WVDI results in relation to the pore structures obtained from the mercury intrusion porosimetry tests of paste samples with the same w/c ratios were analyzed, which provided a basic insight into the moisture distribution in the non-saturated cement mortars. The relative chloride diffusion coefficients of cement mortars at various water saturations were determined based on the Nernst-Einstein equation and conductivity technique. It is found that the relative chloride diffusion coefficient D_rc depends on the degree of water saturation S_w and WVDI. At a given S_w level, the D_rc is larger for a higher w/c ratio. The role of the w/c ratio in the D_rc–S_w relation, however, becomes less pronounced with increasing w/c ratio. There exists a critical saturation, below which the water-filled capillary pores are discontinuous and the D_rc-value tends towards infinitely small. An increase of the w/c ratio results in a decrease of the critical saturation level.