BACKGROUND: The work is focused on the application of vapour phase hydrogen peroxide (VPHP) as a highly promising and effective decontamination technique. The aim of this work was to assess the use of this validated technique for the removal of chemicals from contaminated surfaces and examine the impact of key parameters on the course of the decontamination process. RESULTS: Unique sophisticated laboratory equipment was developed to test the effect of VPHP on chemical substances. It was used for the evaluation of the role of crucial parameters such as the relative humidity, condensation and synergistic effect of UV radiation on the VPHP agent efficiency on a model compound (vanillin) degradation. The degradation rate of the model substance was notably affected by all these factors. CONCLUSION: VPHP could be used for an efficient decomposition of vanillin. The course of the decontamination process was strongly influenced by condensation (showing a substantial difference between 'wet' and 'dry' processes) and the synergistic effect of UV radiation influencing the reaction rate and degree of decomposition. (C) 2010 Society of Chemical Industry