The Large Binocular Telescope (LBT) houses two 8.4-meter mirrors separated by 14.4 meters on a common mount. Coherent combination of these two AO-corrected apertures via the LBT Interferometer (LBTI) produces Fizeau interferometric images with a spatial resolution equivalent to that of a 22.8-meter telescope and the light-gathering power of single 11.8-meter mirror. Capitalizing on these unique capabilities, we used LBTI/LMIRcam to image thermal radiation from volcanic activity on the surface of Io at M-Band (4.8 μm) over a range of parallactic angles. At the distance of Io, the M-Band resolution of the interferometric baseline corresponds to a physical distance of ~135 km, enabling high-resolution monitoring of Io volcanism such as ares and outbursts inaccessible from other ground-based telescopes operating in this wavelength regime. Two deconvolution routines are used to recover the full spatial resolution of the combined images, resolving at least sixteen known volcanic hot spots. Coupling these observations with advanced image reconstruction algorithms demonstrates the versatility of Fizeau interferometry and realizes the LBT as the first in a series of extremely large telescopes.