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In order to meet the demands for the measurement of the electric field vector and its spatial distribution in electrostatic Stark decelerators, velocity filters, guides and traps, etc., we propose a novel approach to measure an electrostatic-field vector and its spatial distribution by using high-sensitive pendular-state spectra of cold linear molecules.New idea of this method is based on the inherent dependences of the intensity of the Q-branch spectrum of cold linear molecules on both the electric-field strength and the molecular rotational temperature.