In this study, Er3+/Al3+ co-doped silica glasses with various Al/Er ratios ranging from 0 to 200 and a constant Er2O3 amount were prepared using the sol-gel method combined with high-temperature vacuum sintering. The absorption, emission spectra, and fluorescence lifetime of Er3+ ions were recorded and the absorption and emission cross sections were calculated. Using Raman, 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS-NMR), 27Al triple-quantum (TQ)-MAS-NMR, and electron paramagnetic resonance (EPR) spectroscopies, the physical and optical properties were correlated with the glass structural modifications due to the Al/Er ratio change. With the increase in the Al/Er ratio, the content of Al3+ ions around the Er3+ ions gradually increased. Meanwhile, the AlO5 and AlO6 polyhedrons increased at the expense of the AlO4 and SiO4 tetrahedrons, which resulted in an improved symmetry and better ionic Er–O bonds. These structural changes led to the site-to-site variations in the Er3+ local environment and the changes in the ligand field strength of the Er–O bonds. This, in turn, resulted in the inhomogeneous broadening of the absorption and emission spectra, with a blue shift of both absorption and emission peaks and a decrease in both absorption and emission at 1.53 μm. With the increase in Al/Er ratio, the full width at half maximum (FWHM) of the emission increased from 27.2 to 54.3 nm. The FWHM × emission cross section (σemi) parameter for evaluating broadband amplification behavior was 30.1 × 10−20 cm2 · nm. This work reveals the close relationship between the glass structure and the spectroscopic properties of Er3+ ions and provides an important reference for the design of broadband amplifier materials in the field of optical communication.