Electrochemical treatment by means of direct current (DC) is usually used as a measure for steel rebar corrosion protection, e.g., cathodic protection (CP), electrochemical chloride extraction (ECE), and re-alkalization (RA). However, the passage of an electrical charge through the pore system of concrete or mortar, coupled with the migration of ions, concentration changes, and resulting phase changes, may alter its chloride penetration resistance and, subsequently, the time until rebar corrosion activation. Porosity changes in hardened Portland cement mortar were studied by means of mercury intrusion porosimetry (MIP) and electrochemical impedance spectroscopy (EIS), and alterations in the mortar surface phase composition were observed by means of X-ray diffraction (XRD). In order to innovatively investigate the impact of DC treatment on the properties of the mortar–electrolyte interface, the cathode-facing mortar surface and the anode-facing mortar surface were analyzed separately. The corrosion of steel coupons embedded in DC-treated hardened mortar was monitored by means of the free corrosion potential (E_oc) and polarization resistance (R_p). The results showed that the DC treatment affected the surface porosity of the hardened Portland cement mortar at the nanoscale. Up to two-thirds of the small pores (0.001–0.01 µm) were replaced by medium-sized pores (0.01–0.06 µm), which may be significant for chloride ingress. Although the porosity and phase composition alterations were confirmed using other techniques (EIS and XRD), corrosion tests revealed that they did not significantly affect the time until the corrosion activation of the steel coupons in the mortar.