In this study, reactive B/Ti nano-multilayers were fabricated by magnetron sputtering and the structure and chemical composition were confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy analyses. The periodic multilayer structure can be clearly visible, and the multilayer material is composed of B layers (amorphous), Ti layers (nano-polycrystalline), and intermixed reactants in a metastable system. The as-deposited B/Ti nano-multilayers exhibit a significantly high heat release of 3722 J/g, with an onset reaction temperature of 449 °C. On the basis of these properties, an integrated microigniter was designed and prepared by integration of the B/Ti nano-multilayers with a TaN film bridge for potential applications in plasma generation, and the electric ignition processes were investigated with discharge voltages ranging from 25 to 40 V. The integrated microigniter exhibits improved and stable ignition performances with a short burst time, high plasma temperature, and violent explosion phenomenon in comparison with the TaN film igniter. Overall, the plasma generation of the microigniter can be enhanced substantially by integration with the B/Ti nano-multilayers.