In the Internet of Things (IoT) era, various devices (e.g., sensors, actuators, energy harvesters, etc.) and systems have been developed toward the realization of smart homes/buildings and personal health care. These advanced devices can be categorized into ambient devices and wearable devices based on their usage scenarios, to enable motion tracking, health monitoring, daily care, home automation, fall detection, intelligent interaction, assistance, living convenience, and security in smart homes. With the rapidly increasing number of such advanced devices and IoT systems, achieving fully self-sustained and multimodal intelligent systems is becoming more and more important to realize a sustainable and all-in-one smart home platform. Hence, in this Review, we systematically present the recent progress of the development of advanced materials, fabrication techniques, devices, and systems for enabling smart home and health care applications. First, advanced polymer, fiber, and fabric materials as well as their respective fabrication techniques for large-scale manufacturing are discussed. After that, functional devices classified into ambient devices (at home ambiance such as door, floor, table, chair, bed, toilet, window, wall, etc.) and wearable devices (on body parts such as finger, wrist, arm, throat, face, back, etc.) are presented for diverse monitoring and auxiliary applications. Next, the current developments of self-sustained systems and intelligent systems are reviewed in detail, indicating two promising research directions in this field. Last, conclusions and outlook pinpointed on the existing challenges and opportunities are provided for the research community to consider.