In this work, bismuth doped fiber (BDF) and bismuth/phosphosilicate co-doped fiber (BPDF) were fabricated by atomic layer deposition (ALD) combined with the modified chemical vapor deposition (MCVD). The spectral characteristics are studied experimentally and the BPDF has good excitation effect covering the O band. A diode pumped BPDF amplifier with the gain over 20 dB from 1298-1348 nm (50 nm) has been demonstrated. The maximum gain of 30 dB was measured at 1320 nm with a gain coefficient of around 0.5 dB/m. Furthermore, we constructed different local structures through simulation and found that compared with the BDF, BPDF has a stronger excited state and a greater significance in O-band. This is mainly because phosphorus (P) doping changes the associated electron distribution and forms the bismuth-phosphorus active center. The fiber has a high gain coefficient, which is of great significance for the industrialization of O-band fiber amplifier.