This paper deals with an experimental study of the flexural behavior of sustainable reinforced cement concrete (RCC) beams with a smart mortar layer attached to the concrete mixture. In total, nine RCC beams were cast and tested. Two types of reinforced concrete beams were cast, and three different beams of sizes 1000 × 150 × 200 mm and six different beams of sizes 1500 × 100 × 250 mm were considered. The flexural behavior of these RCC beams was studied in detail. The electrical resistivity of these beams was also calculated, which was derived from the smart mortar layer. Research on the application of smart mortars within structural members is limited. The experimental results showed that the smart mortar layer could sense the damage in the RCC beams and infer the damage through the electrical measurement values, making the beam more sustainable. It was also observed that the relationship between the load and the fractional change in electrical resistance was linear. The fractional change in electrical resistivity was found to steadily increase with the increase in initial loading. A significant decrease in the fractional change in electrical resistivity was seen as the load approached failure. When a layer of mortar with brass fiber was added to the mortar paste, the ultimate load at failure was observed and compared with the reference beam specimen using Araldite paste. Compared to the hybrid brass-carbon fiber-added mortar layer, the brass fiber-added mortar layer increased the fractional change in the electrical resistivity values by 14–18%. Similarly, the ultimate load at failure was increased by 3–8% in the brass fiber-added mortar layer when compared to the hybrid brass-carbon fiber-added mortar layer. Failure of the beam was indicated by a sudden drop in the fractional change in electrical resistivity values.