A field study on the estimation and analysis of iron stability in drinking water distribution system was carried out in a city of China. The stability of iron ion was estimated by pC-pH figure. It was found that iron ion was unstable, with a high Fe(OH)3 precipitation tendency and obvious increases in turbidity. The outer layer of the scale was compact, while the inner core was porous. The main composition of the scale was iron, and the possible compound constitutes of the outer scale were α-FeOOH, γ-FeOOH, α-Fe2O3, γ-Fe2O3 and FeCl3, while that of the inner scale were Fe3O4, FeCl2 and FeCO3. According to the characteristics of the corrosion scale, it was thought that the main reason for iron instability was iron release from corrosion scale. Many factors such as pipe materials, dissolved oxygen and chlorine residual affect iron release. Generally, higher iron release occurred with lower dissolved oxygen or chlorine residual concentration, while lower iron release occurred with higher dissolved oxygen or chlorine residual concentration. The reason was considered that the passivated out layer of scale of ferric oxide was broken down by reductive reaction in a condition of low oxidants concentration, which would result more rapid corrosion of the pipe and red water phenomenon.