Two series of Yb3+-doped silica glasses (YA and YAP) are fabricated using the sol-gel method, and their spectroscopic properties are investigated. The longest fluorescence lifetime of 0.96 ms is obtained in YAP2 and YAP3 glasses. The emission cross-section (emi) and emi × of Yb3+ in the YAP1 glass are 1.00 pm2 and 0.94 pm2·ms, respectively. Co-doping with Al and P decreases the hydroxyl group content in the glasses because of the reduction in non-bridging oxygen content. The lowest OH content in the YAP3 glass is 9.6 ppm.