Solid electrolytes have great potential to address the safety issues of Li-ion batteries, but better synthesis methods are still required for ceramics such as lithium lanthanum titanate (LLTO) since current techniques require high-temperature calcination for long times. Here we report a new approach that utilizes electrospinning to prepare phase-pure polycrystalline LLTO nanowires with well-crystallized tetragonal structure after only 3 h calcination at 1000 °C. Pellets prepared from the electrospun LLTO nanowires had higher density, less void space, and higher Li+ conductivity compared to those comprised of LLTO prepared with conventional sol–gel methods. This work demonstrates the potential that electrospinning can provide towards improving the properties of sol–gel derived ceramics.