Hydrogen peroxide is a precursor to damage mechanisms in numerous applications; its monitoring is important and challenging. The effect of temperature on the performance and durability of a recently developed optical fiber sensors sensitive to the presence of hydrogen peroxide in low concentrations is investigated. The sensors are fabricated by immobilizing Prussian blue within a multilayer of electrostatically self-assembled polyelectrolytes. The sensing principle of this optical electrode relies on the change in the intensity of the reflected light when Prussian white is oxidized back to the blue state due to the presence of hydrogen peroxide. The amplitude of the intensity of the reflected light is found to vary with temperature in a quadratic fashion, but the characteristic response time which correlates with concentration remains constant. Thus the sensing device retains its abilities to determine and quantify the concentration of hydrogen peroxide in a liquid solution. Additionally, the degradation of these fiber sensors when subjected to high temperature is examined. Four optical fiber sensing devices were subjected to different testing conditions and a characterization protocol that included: measurement of the intensity of the cyanide stretch (2150 cm(-1)) via Raman micro spectroscopy; imaging with scanning electron microscopy; and measurement of the presence of iron ions using energy dispersive X-ray spectroscopy. The results show a gradual degradation of the sensing device as a result of progressive desorption of the polyelectrolyte multilayer structure that leads to leaching of the Prussian reagent. This degradation mechanism does not compromise the functionality of the device which is found sufficiently robust for multiple tests at high temperature. The simplicity of this sensing system combined with its relative robustness and reusability make it a good a good candidate for minimally intrusive and localized monitoring of hydrogen peroxide formation in operating PEMFCs. (C) 2014 Elsevier Ltd. All rights reserved.