The industrial Internet of things (IIoT) is a major lever in Industry 4.0 development, where reducing the carbon footprint and energy consumption has become crucial for modern companies. Today’s IIoT device infrastructure wastes large amounts of energy on wireless communication, limiting device lifetime and increasing power consumption and battery requirements. Communication capabilities seriously affect the responsiveness and availability of autonomous IoT devices when collecting data and retrieving commands to/from higher-level applications. Thus, the objective of optimizing communication remains paramount; in addition to typical optimization methods, such as algorithms and protocols, a new concept is emerging, known as wake-up radio (WuR). WuR provides novel on-demand radio communication schemes that can increase device efficiency. By expanding the lifespan of IoT devices while maintaining high reactivity and communication performance, the WuR approach paves the way for a “place-and-forget” IoT device deployment methodology that combines a small carbon footprint with an extended lifetime and highly responsive functionality. WuR technology, when applied to IoT devices, facilitates green IIoT, thereby enabling the emergence of a novel on-demand IoT (OD-IoT) concept. This article presents an analysis of the state-of-the-art WuR technology within the green IoT paradigm and details the OD-IoT concept. Furthermore, this review provides an overview of WuR applications and their impact on the IIoT, including relevant industry use cases. Finally, we describe our experimental performance evaluation of a WuR-enabled device that is commercially available off the shelf. Specifically, we focused on the communication range and energy consumption, successfully demonstrating the applicability of WuR and the strong potential that it has and the benefits that it offers for sustainable IIoT systems.