Energy harvesting and energy storage are two most important technologies in today's green and renewable energy science. As for energy harvesting, the fundamental science and practically applicable technologies are not only essential in realizing the self-powered electronic devices and systems, but also tremendously helpful in meeting the rapid-growing world-wide energy consumptions. Mechanical energy is one of the most universally-existing, diversely-presenting, but usually-wasted energies in the natural environment. Owing to the limitations of the traditional technologies for mechanical energy harvesting, it is highly desirable to develop new technology that can efficiently convert different types of mechanical energy into electricity. On the other hand, the electricity generated from environmental energy often needs to be stored before used to drive electronic devices. For the energy storage units such as Li-ion batteries as the power sources, the limited lifetime is the prominent problem. Hybridizing energy harvesting devices with energy storage units could not only provide new solution for this, but also lead to the realization of sustainable power sources. In this dissertation, the research efforts have led to several critical advances in a new technology for mechanical energy harvesting—triboelectric nanogenerators (TENGs). Previous to the research of this dissertation, the TENG only has one basic mode—the contact mode. Through rational structural design, we largely improved the output performance of the contact-mode TENG and systematically studied their characteristics as a power source. Beyond this, we have also established the second basic mode for TENG—the lateral sliding mode, and demonstrated sliding-based disk TENGs for harvesting rotational energy and wind-cup-based TENGs for harvesting wind energy. In order to expand the application and versatility of TENG by avoid the connection of the electrode on the moving part, we further developed another basic mode—freestanding-layer mode, which is capable of working with supreme stability in non-contact mode and harvesting energy from any free-moving object. Both the grating structured and disk-structured TENGs based on this mode also display much improved long-term stability and very high energy conversion efficiency. For the further improvement of the TENG’s output performance from the material aspect, we introduced the ion-injection method to study the maximum surface charge density of the TENG, and for the first time unraveled its dependence on the structural parameter—the thickness of the dielectric film. The above researches have largely propelled the development of TENGs for mechanical energy harvesting and brought a big potential of impacting people’s everyday life. Targeted at developing sustainable and independent power sources for electronic devices, efforts have been made in this dissertation to develop new fundamental science and new devices that hybridize the nanogenerator-based mechanical energy harvesting and the Li-ion-battery-based energy storage process into a single-step process or in a single device. Through hybridizing a piezoelectric nanogenerator with a Li-ion battery, a self-charging power cell has been demonstrated based on a fundamentally-new mechanical-to-electrochemcial process. The triboelectric nanogenerator as a powerful technology for mechanical energy harvesting has also been hybridized with a Li-ion battery into a self-charging power unit. This new concept of device can sustainably provide a constant voltage for the non-stop operation of electronic devices.