Nanoglasses are solids consisting of nanometer-sized glassy regions connected by interfaces having a reduced density. We studied the structure of Sc(75)Fe(25) nanoglasses by electron microscopy, positron annihilation spectroscopy, and small-/wide-angle X-ray scattering. The positron annihilation spectroscopy measurements showed that the as-prepared nanoglasses consisted of 65 vol% glassy and 35 vol% interfacial regions. By applying temperature annealing to the nanoglasses and measuring in situ small-angle X-ray scattering, we observed that the width of the interfacial regions increased exponentially as a function of the annealing temperature. A quantitative fit to the small-angle X-ray scattering data using a Debye-Bueche random phase model gave a correlation length that is related to the sizes of the interfacial regions in the nanoglass. The correlation length was found to increase exponentially from 1.3 to 1.7 nm when the sample temperature was increased from 25 to 230 °C. Using simple approximations, we correlate this to an increase in the width of interfacial regions from 0.8 to 1.2 nm, while the volume fraction of interfacial regions increased from 31 to 44%. Using micro-compression measurements, we investigated the deformation behavior of ribbon glass and the corresponding nanoglass. While the nanoglass exhibited a remarkable plasticity even in the annealed state owing to the glass-glass interfaces, the corresponding ribbon glass was brittle. As this difference seems not limited to Sc(75)Fe(25) glasses, the reported result suggest that nanoglasses open the way to glasses with high ductility resulting from the nanometer sized microstructure.