Grain boundaries (GBs) play an important role in material behavior, so considerable effort has gone into determining their structure and properties. Studies of GBs have revealed a correlation between the GB energy and expansion of the planes normal to the GB, or the so-called normal volume expansion. In this investigation, the volume expansion at several GBs was experimentally determined using extended energy-loss fine structure (EXELFS) analysis in a scanning/transmission electron microscope, allowing changes in the nearest-neighbor (n.n.) distances to be determined with nanometer spatial resolution. EXELFS performed on three-model GBs showed that the average n.n. distances at the GBs increased with increasing GB energy. Additionally, the total volume expansion at the GBs, calculated using complementary plasmon energy profiles, showed excellent agreement with volume expansions measured using other experimental techniques. Hence, this study demonstrates that EXELFS is a useful technique to measure the normal volume expansion at GBs. When combined with the results from complementary studies on the same GBs using valence electron energy-loss spectroscopy, this work further shows that the GB energy increases in relation to both the decrease in electron density at the GB and an accompanying increase in specific volume expansion at the GB.