Structure determination of glass remains an important issue in glass science. The electron microscope with its high spatial resolution and versatile functions has been widely applied to observe phase separation and structural heterogeneity in glass. While elemental analysis such as energy dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS) may provide local compositional information with nanometer-scale resolution, structural information in a glass network cannot be directly obtained. Here, a novel way to probe local coordination is employed using electron energy loss fine structure (ELNES) in the scanning transmission electron microscope (STEM). The method is demonstrated in a phase-separated aluminosilicate glass with multiple Al-coordinated species. With the support of ab initio calculation, two exciton-like peaks in the Al L2,3-edge at around 77 and 80 eV are attributed to 4-fold and 5,6-fold Al excitations, respectively. Mapping of the relative intensity ratio for two peaks in a phase-separated microstructure reveals a heterogeneous distribution of highly coordinated Al species in real space. The finding is in agreement with previous MD simulation that 5- and 6-fold Al species are favored to form in the Al-rich phase. This work has demonstrated that complex network structure within the phase-separated region can now be studied via STEM-EELS.