Radio frequency (rf) sputtered films of 10 at. % P2O5-doped zinc oxide (ZnO) were deposited at temperatures (Td) below the sublimation point of P2O5 (Td≪350 °C) and at a range of oxygen pressures p(O2). Ultraviolet-visible optical transmission measurements, x-ray photoelectron spectroscopy (XPS), and x-ray diffraction were used to examine the effects of p(O2) during deposition on the band gap and on the bonding behavior of phosphorus. At both deposition temperatures studied (room temperature with unintentional heating and 125 °C), an increase in phosphorus concentration with increasing p(O2) was observed. However, the dependence of the band gap behavior on p(O2) was observed to be dramatically different for the two deposition temperatures: room-temperature-deposited films show a redshift while films deposited at 125 °C show a blueshift. Analysis of the oxygen 1s XPS peak shows a progressive formation of nonbridging (Zn–O–P) bond networks for room temperature films, whereas films grown at 125 °C show increased (P–O–P) bond networks with increasing p(O2). This indicates that a small degree of thermal activation considerably modifies the bonding behavior of phosphorus in ZnO. Implications of these results for the use of phosphorus as a p-type dopant for Z- nO are discussed.