This study addressed an important but not yet thoroughly investigated topic regarding human exposure to radio-frequency electromagnetic fields (RF-EMF) generated by vehicular connectivity. In particular, the study assessed, by means of computational dosimetry, the RF-EMF exposure in road users near a car equipped with vehicle-to-vehicle (V2V) communication antennas. The exposure scenario consisted of a 3D numerical model of a car with two V2V antennas, each fed with 1 W, operating at 5.9 GHz and an adult human model to simulate the road user near the car. The RF-EMF dose absorbed by the human model was calculated as the specific absorption rate (SAR), that is, the RF-EMF power absorbed per unit of mass. The highest SAR was observed in the skin of the head (34.7 mW/kg) and in the eyes (15 mW/kg); the SAR at the torso (including the genitals) and limbs was negligible or much lower than in the head and eyes. The SAR over the whole body was 0.19 mW/kg. The SAR was always well below the limits of human exposure in the 100 kHz–6 GHz band established by the International Commission on Non-Ionizing Radiation Protection (ICNIRP). The proposed approach can be generalized to assess RF-EMF exposure in different conditions by varying the montage/number of V2V antennas and considering human models of different ages.