One of the ways of lessening the CO2 emissions of cement industry consists of replacing clinkers with supplementary cementitious materials. The required service life of real construction elements is long, so it is useful to characterize the performance of these materials in the very long term. Here, the influence of incorporating waste glass powder as a supplementary cementitious material, regarding the microstructure and durability of mortars after 1500 hardening days (approximately 4 years), compared with reference mortars without additions, was studied. The percentages of clinker replacement by glass powder were 10% and 20%. The microstructure was studied using impedance spectroscopy and mercury intrusion porosimetry. Differential thermal and X-ray diffraction analyses were performed for assessing the pozzolanic activity of glass powder at the end of the time period studied. Water absorption after immersion, the steady-state diffusion coefficient, and length change were also determined. In view of the results obtained, the microstructure of mortars that incorporated waste glass powder was more refined compared with the reference specimens. The global solid fraction and pores volume were very similar for all of the studied series. The addition of waste glass powder reduced the chloride diffusion coefficient of the mortars, without worsening their behaviour regarding water absorption after immersion.