Hot conditioning operation of the primary heat transport system is an important step prior to the commissioning of Pressurized Heavy Water Reactors. One of the major objectives of the operation is to develop a stable and protective magnetite layer on the inner surfaces of carbon steel piping. The correlation between stable magnetite film growth on carbon steel surfaces and the period of exposure to hot conditioning environment is generally established by a combination of weight change measurements and microscopic/morphological observations of the specimens periodically removed during the operation. In the present study, electrochemical impedance spectroscopy (EIS) at room temperature is demonstrated as an alternate, quantitative technique to arrive at an optimal duration of the exposure period. Specimens of carbon steel were exposed for 24, 35 and 48 h during hot conditioning of primary heat transport system of two Indian PHWRs. The composition and morphology of oxide films grown during exposure was characterized by X-ray diffraction and optical microscopy. Further, ex situ electrochemical impedance spectra of magnetite films formed after each exposure were measured, in 1 ppm Li⁺ electrolyte at room temperature as a function of potential in a range of -0.8 to +0.3 V_SCE. The defect density of the magnetite films formed after each exposure was estimated by Mott–Schottky analysis of capacitances extracted from the impedance spectra. Further the ionic resistance of the oxide was also extracted from the impedance spectra. Defect density was observed to decrease with increase in exposure time and to saturate after 35 h, indicating stabilisation of the barrier layer part of the magnetite film. The values of the ionic transport resistance start to increase after 35–40 h of exposure. The quantitative ability of EIS technique to assess the film quality demonstrates that it can be used as a supplementary tool to the thickness and morphological characterizations of samples during hot conditioning.