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In order to improve the performance of the LIBS technique -in particular its sensitivity, reproducibility and limit of detection -we studied the effect of applying a static electric field with different polarities on the emission spectra obtained in a typical LIBS set-up. The physical parameters of the laserinduced plasma, namely the electron density N e and the plasma temperature T e , were studied under such circumstances. In addition to the spectroscopic analysis of the plasma plume emission, the laser-induced shock waves were exploited to monitor the probable changes in the plasma plume dynamics due to the application of the electric field. The study showed a pronounced enhancement in the signal-to-noise (S/N) ratio of different Al, neutral and ionic lines under forward biasing voltage (negative target and positive electrode). On the other hand, a clear deterioration of the emission line intensities was observed under conditions of reversed polarity. This negative effect may be attributed to the reduction in electron-ion recombinations due to the stretched plasma plume. The plasma temperature showed a constant value in the average with the increasing electric field in both directions. This effect may be due to the fact that the measured values of T e were averaged over the whole plasma emission volume. The electron density was observed to decrease slightly in the case of forward biasing while no significant effect was noticed in the case of reversed biasing. This slight decrease in N e can be interpreted in view of the increase in the rate of electron-ion recombinations due to the presence of the electric field. No appreciable effects of the applied electric field on the plasma dynamics were noticed.