Bis-piperidiniummethyl-urea (BPMU) was developed as a volatile corrosion inhibitor (VCI) for mild steel. Its vapor corrosion inhibition property was evaluated by volatile inhibiting sieve test (VIS). Electrochemical measurements were conducted in simulated atmospheric corrosion water. Electrochemical impedance spectroscopy of a volatile corrosion inhibitor monitor cell (VCIM) was applied to study the effect of BPMU on the corrosion inhibition of mild steel under a thin electrolyte layer. The results show that BPMU has good protection effect for steel. It suppressed the anodic reaction of the steel electrode in a manner of promoted passivation. Fourier transform infrared (FT-IR) spectroscopy was used to characterize the adsorption of BPMU on the steel surface.