Corrosion of reinforcing steel generated by chloride penetration is one of the main causes of deterioration of reinforced concrete structures. One of the best ways to control deterioration in structures due to this process is through quality control of the concrete before use. The capillary porosity and migration give parameters that could be related to material durability mechanisms. In this case, the Standard test method for density, absorption, and Voids in hardened concrete (ASTM C642:13), the Standard Test method for electrical indication of concrete's Ability to Resist Chloride ion Penetration (ASTM C1202:19) and the Chloride migration coefficient from non-steady-state (NT BUILD 492:99) provide procedures for determining parameters to characterize the ability of concrete to resist chloride penetration. However, these tests are difficult, time-consuming, and expensive to perform. Therefore, in recent years the formation factor (F) has emerged as an alternative to develop tests that allow concrete to be evaluated in an easy, fast, and economic way. The formation factor (F) comes from Archie's Law, and it is a dimensionless factor that allows us to relate the resistivity of a rock, with its porosity and with the resistivity of the fluid contained in it. This factor has been used successfully to characterize some properties of concrete. In that order of ideas, in this paper the capillary porosity, the chloride penetrability and the chloride migration coefficient of mortar mixtures with different percentages of addition of silica fume (SF) were characterized by the Formation Factor (F). For this purpose, Portland cement was partially mixed with Silica fume (SF) up to 15%, in four different mortar mixtures, and for the measurement of the Bulk resistivity of mortar samples (p), electrochemical impedance spectroscopy (EIS) was used. Additionally, tests of compressive strength, and Bulk density were carried out. A new experimental method based on electrochemical impedance spectroscopy (EIS) to characterize capillary porosity and chloride penetration in cement-based materials is proposed. Finally, this paper shows a strong correlation between the formation factor (F) and the capillary porosity, the chloride penetration and the compressive strength properties of silica fume mortars, which could be used as a parameter for quality control of cement-based materials. Further studies on this subject are highly recommended.