Naturally biological materials, such as wood and bamboo, have unique and sophisticated structures after evolution by nature through ages. Bamboo is the most abundant plant in China and other tropical countries. Upon carbonization of bamboo, economically important and environmentally friendly bamboo charcoal is produced. Bamboo charcoal contains a considerable amount of mineral elements, acting as effective catalysts for growing carbon nanotubes (CNTs) at high temperatures (1200–1400°C). This eliminates the use of transition metal catalysts commonly used for the synthesis of CNTs. In this chapter, the preparation, structure, and application of novel, low-cost, and multifunctional composites of CNT/bamboo charcoal are discussed in details. Particular attention is paid to the chemical vapor deposition of CNTs from bamboo charcoals at both low and high temperatures.