Nitrite is known to accumulate in wastewater treatment plants (WWTPs) under certain environmental conditions. The protonated form of nitrite, free nitrous acid (FNA), has been found to cause severe inhibition to numerous bioprocesses at WWTPs. However, this inhibitory effect of FNA may possibly be gainfully exploited, such as repressing nitrite oxidizing bacteria (NOB) growth to achieve N removal via the nitrite shortcut. However, the inhibition threshold of FNA to repress NOB (similar to 0.02 mg HNO(2)-N/L) may also inhibit other bioprocesses. This paper reviews the inhibitory effects of FNA on nitrifiers, denitrifiers, anammox bacteria, phosphorus accumulating organisms (PAO), methanogens, and other microorganisms in populations used in WWTPs. The possible inhibition mechanisms of FNA on microorganisms are discussed and compared. It is concluded that a single inhibition mechanism is not sufficient to explain the negative impacts of FNA on microbial metabolisms and that multiple inhibitory effects can be generated from FNA. The review would suggest further research is necessary before the FNA inhibition mechanisms can be more effectively used to optimize WWTP bioprocesses. Perspectives on research directions, how the outcomes may be used to manipulate bioprocesses and the overall implications of FNA on WWTPs are also discussed.