In this study, porosity assessment of cement mortars containing Precious Slag (PS) Ball–an industrial waste produced by rapid cooling of slag generated from steel making process by Slag Atomizing Technology–is done by Back-Scattered Electron (BSE) image analysis. PS incorporated mortars were fabricated and subsequently evaluated for compressive strength. BSE images were analyzed by pore segmentation method. Binarization on the images using Otsu’s thresholding method was done followed by the porosity determination. As the interfacial attributes were the primary concern, the porosity was determined from the aggregate surface to the 100 μm width. A total of 24 sections were analyzed and the mean values were plotted. Although the PS Ball incorporated mortar exhibited 10% lower strength at 28-day age, it showed stronger and less porous aggregate- matrix interface between (from particle surface up to 35 μm width) as compared to that of normal mortar containing sand, which is justifiable by the chemical composition of PS Ball attributed to the potential chemical binding. Further, the porosity decreased as the distance from aggregate surface increased. While the use of PS Ball is environmentally friendly, its enhanced interfacial properties with some strength loss of resulting cement mortars encourages its use in sustainable construction materials.