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This work focuses upon the effects of DC electric fields on the stability of downward propagating atmospheric pressure premixed propane–air flames under experimental conditions that provide close coupling of the electric field to the flame. With the appropriate electrode geometry, modest applied voltages are shown to drive a stable conical flame first into a wrinkled-laminar flamelet geometry, and then further toward either a highly unstable distributed flamelet regime or a collective oscillation of the flame front. Applied potentials up through +5 kV over a 40-mm gap encompassing the flame front have been used to force the above transition sequence in flames with equivalence ratios between 0.8 and 1.3 and flow velocities up to 1.7 m/s. Experiments are reported that characterize the field-induced changes in the geometry of the reaction zone and the structure of the resulting unstable flame. The former is quantified by combustion intensity enhancement estimates derived from high-speed two-dimensional direct and spectroscopic imaging of chemiluminescence signals. The flame fluid mechanical response to the applied field, brought about by forcing positive flame ions counter to the flow, drives the effective flame Lewis number to values suitable for the onset of the thermodiffusive instability, even near stoichiometric conditions. Possible field-driven flame ion recombination chemistry that would produce light reactants near the burner head and precipitate the onset of the thermodiffusive instability is proposed. Electrical measurements are also reported that establish that minimal electrical power input is required to produce the observed flame instabilities. Current continuity-based calculations allow estimates of the level of deficient light reactant necessary to cause the flame to become unstable. This applied-electric-field-induced modification of the thermodiffusive effect could serve as a potentially attractive means of controlling flame fluid-mechanical characteristics and validating combustion instability models over a wide range of equivalence ratios.