(1) Background: Cooperative Intelligent Transportation Systems (C-ITS) will soon operate using 5G New-Radio (NR) wireless communication, overcoming the limitations of the current V2X (Vehicle-to-Everything) wireless communication technologies and increasing road-safety and driving efficiency. These innovations will also change the RF exposure levels of pedestrians and road-users in general. These people, in fact, will be exposed to additional RF sources coming from nearby cars and from the infrastructure. Therefore, an exposure assessment of people in the proximity of a connected car is necessary and urgent. (2) Methods: Two array antennas for 5G-V2X communication at 3.5 GHz were modelled and mounted on a realistic 3D car model for evaluating the exposure levels of a human model representing people on the road near the car. Computational simulations were conducted using the FDTD solver implemented in the Sim4Life platform; different positions and orientations between the car and the human model were assessed. The analyzed quantities were the Specific Absorption Rate on the whole body (SARwb), averaged over 10 g (SAR10g) in specific tissues, as indicated in the ICNIRP guidelines. (3) Results: the data showed that the highest exposure levels were obtained mostly in the head area of the human model, with the highest peak obtained in the configuration where the main beam of the 5G-V2X antennas was more direct towards the human model. Moreover, in all configurations, the dose absorbed by a pedestrian was well below the ICNIRP guidelines to avoid harmful effects. (4) Conclusions: This work is the first study on human exposure assessment in a 5G-V2X scenario, and it expands the knowledge about the exposure levels for the forthcoming use of 5G in connected vehicles.