In this work, new spectroscopic techniques have been developed to measure electric dipole moments of highly excited rovibrational states of small polyatomic molecules in the gas phase. These techniques make use of lasers arid of microwave synthesizers. They enable one to measure the change on a molecular system caused by applying an external electric field, which is called Stark effect and from this, extract the dipole moment. The first technique, called microwave Stark spectroscopy, makes use of microwave-optical double resonance combined to either laser induced fluorescence or vibrational predissociation detection. The second approach, called Stark induced quantum beat spectroscopy, relies on the time evolution of a coherently prepared molecular wavepacket in an electric field, using either electronic photodissociation or laser induced fluorescence for detection. These techniques have been applied to H2C0, HOCl, HDO, and H20 for whom the electric dipole moment have been measured for several highly excited rovibrational states of the ground electronic state. Using these experimental measurements, the dependence of the dipole moment vector, both in orientation and in magnitude, on the vibrational excitation is discussed. Moreover the experimental data are used to test ab initio calculations potential energy and dipole moment surfaces and to establish critical benchmarks for future improvements. Due to the rarity of dipole moment data for highly excited vibrational states and their central role in transition intensities, intermolecular forces and collisions, these measurements are of special importance for chemical and energy transfer processes in atmospheric sciences, combustion studies, planetology, or more generally in the whole quantitative spectroscopy field, where transitions intensities are at least as important as line frequency positions.