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, Al-27 and Si-29 magic angle spinning nuclear magnetic resonance (MAS-NMR), Al-27 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 mu m. With the increase in Al/Er ratio, the full width at half maximum (FWHM) of the emission increased from 27.2 to 54.3nm. The FWHMxemission cross section (sigma emi) parameter for evaluating broadband amplification behavior was 30.1x10(-20)cm(2).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.