5G New Radio (NR) is touted as a pivotal enabling technology for the genuine realization of connected and cooperative autonomous driving. Despite numerous research efforts in recent years, a systematic overview on the role of 5G NR in future connected autonomous communication networks is missing. To fill this gap and to spark more future research, this article introduces the technology components of 5G NR and discusses the evolution from existing cellular vehicle-to-everything (V2X) technology toward NR-V2X. We primarily focus on the key features and functionalities of the physical layer, sidelink communication and its resource allocation, architecture flexibility, security and privacy mechanisms, and precise positioning techniques. Moreover, we envisage and highlight the potential of machine learning for further performance enhancement in NR-V2X services. Lastly, we show how 5G NR can be configured to support advanced V2X use cases.