Bismuth‐doped glasses are attractive materials for the development of new optical amplifiers and tunable laser sources. In this paper, Bi‐doped phosphosilicate glasses are prepared using the sol‐doping technique in combination with shaping using cold isostatic pressing. After a first drawing at high temperature (2000 °C), the obtained glass cane presents a wide near infrared (NIR) photoluminescence band under visible excitation. The authors show that this NIR optical activity, connected to phosphorus center, is preserved after a second drawing into a conventional optical fiber. These results confirm the potentialities of this synthesis approach for the fabrication of Bi‐activated optical fibers.