Energy harvesting is a technology for generating electrical power from ambient or wasted energy. It has been investigated extensively as a means of powering small electronic devices. The recent proliferation of devices with ultra-low power consumption - devices such as RF transmitters, sensors, and integrated chipsets - has created new opportunities for energy harvesters. There is a variety of ambient energies such as vibration, thermal, solar, stray current, etc. Depending on energy sources, different kinds of energy conversion mechanism should be employed. For energy harvesters to become practical, their energy conversion efficiency must improve. This efficiency depends upon advances in two areas: the system or structural design of the energy harvester, and the properties of the materials employed in energy conversion. This dissertation explores developments in both areas. In the first area, the role of nano-, micro-, and bulk structure of the energy conversion materials were investigated. In the second area, piezoelectric energy harvesters and a magneto-thermoelectric generator are treated from the perspective of system design. In the area of materials development, PbTiO3 (PTO) nanostructures consisting of nanofibers and three-dimensional (3-D) nanostructure arrays were hydrothermally synthesized. The growth mechanism of the PTO nanofibers and 3-D nanostructures were investigated experimentally and theoretically. The PTO nanostructures were composed of oriented PTO crystals with high tetragonality; these arrays could be promising candidates for nanogenerators. Different designs for energy harvesters were explored as a means of improving energy conversion efficiency. Piezoelectric energy harvesters were designed and constructed for applications with a low frequency vibrational energy and for applications with a broadband energy spectrum. A spiral MEMS piezoelectric energy harvester design was fabricated using a silicon MEMS process and demonstrated to extract high power density at ultra-low resonance frequencies and low acceleration conditions. For a broadband energy harvester, a magnetically-coupled array of oscillators was designed and built that broadened the harvester's effective resonance frequency with considerably improved output power. A new design concept for thermal energy harvesting that employs a magneto-thermoelectric generator (MTG) design was proposed. The MTG exploits a thermally-induced second order phase transition in a soft magnetic material near the Curie temperature. The MTG harvested electric power from oscillations of the soft magnet between hot and cold sources. For the MTG design, suitable soft magnetic materials were selected and developed using La0.85Sr0.15MnO3-Ni0.6Cu0.2Zn0.2Fe2O4 magnetic composites. The MTG was fabricated from a PVDF cantilever and a gadolinium (Gd) soft magnetic material. The feasibility of the design for harvesting energy from the waste heat was demonstrated by attaching an MTG array to a computer CPU. / PHD