Triboelectrification is an effect that is known to each and every one probably since ancient Greek time, but it is usually taken as a negative effect and is avoided in many technologies. We have recently invented a triboelectric nanogenerator (TENG) that is used to convert mechanical energy into electricity by a conjunction of triboelectrification and electrostatic induction. As for this power generation unit, in the inner circuit, a potential is created by the triboelectric effect due to the charge transfer between two thin organic/inorganic films that exhibit opposite tribo-polarity; in the outer circuit, electrons are driven to flow between two electrodes attached on the back sides of the films in order to balance the potential. Since the most useful materials for TENG are organic, it is also named organic nanogenerator, which is the first using organic materials for harvesting mechanical energy. In this paper, we review the fundamentals of the TENG in the three basic operation modes: vertical contact-separation mode, in-plane sliding mode, and single-electrode mode. Ever since the first report of the TENG in January 2012, the output power density of TENG has been improved 5 orders of magnitude within 12 months. The area power density reaches 313 W/m(2), volume density reaches 490 kW/m(3), and a conversion efficiency of ∼60% has been demonstrated. The TENG can be applied to harvest all kinds of mechanical energy that is available but wasted in our daily life, such as human motion, walking, vibration, mechanical triggering, rotating tire, wind, flowing water, and more. Alternatively, TENG can also be used as a self-powered sensor for actively detecting the static and dynamic processes arising from mechanical agitation using the voltage and current output signals of the TENG, respectively, with potential applications for touch pad and smart skin technologies. To enhance the performance of the TENG, besides the vast choices of materials in the triboelectric series, from polymer to metal and to fabric, the morphologies of their surfaces can be modified by physical techniques with the creation of pyramid-, square-, or hemisphere-based micro- or nanopatterns, which are effective for enhancing the contact area and possibly the triboelectrification. The surfaces of the materials can be functionalized chemically using various molecules, nanotubes, nanowires, or nanoparticles, in order to enhance the triboelectric effect. The contact materials can be composites, such as embedding nanoparticles in a polymer matrix, which may change not only the surface electrification but also the permittivity of the materials so that they can be effective for electrostatic induction. Therefore, there are numerous ways to enhance the performance of the TENG from the materials point of view. This gives an excellent opportunity for chemists and materials scientists to do extensive study both in the basic science and in practical applications. We anticipate that a better enhancement of the output power density will be achieved in the next few years. The TENG is possible not only for self-powered portable electronics but also as a new energy technology with potential to contribute to the world energy in the near future.