Carbon nanotubes (CNTs) have attracted great attentions in the field of electronics, sensors, healthcare, and energy conversion. Such emerging applications have driven the carbon nanotube research in a rapid fashion. Indeed, the structure control over CNTs has inspired an intensive research vortex due to the high promises in electronic and optical device applications. Here, this in-depth review is anticipated to provide insights into the controllable synthesis and applications of high-quality CNTs. First, the general synthesis and post-purification of CNTs are briefly discussed. Then, the state-of-the-art electronic device applications are discussed, including field-effect transistors, gas sensors, DNA biosensors, and pressure gauges. Besides, the optical sensors are delivered based on the photoluminescence. In addition, energy applications of CNTs are discussed such as thermoelectric energy generators. Eventually, future opportunities are proposed for the Internet of Things (IoT) oriented sensors, data processing, and artificial intelligence.