The solution parameters associated with gradient elution reversed phase high-performance liquid chromatography (HPLC) were characterized by evaluating the electrospray ionization mass spectrometry (ESIMS) response of selected smokeless powder additives. Using direct liquid infusion, the positive ion ESIMS responses were determined for three general classes of powder constituents: dialkylphthalate acid esters, N,N'-dialkyl-N,N'-diphenyl urea based stabilizers and nitroso-, nitro-, and dinitro- derivatives of diphenylamine. The relative ESIMS intensities of the powder components were investigated as a function of three solution parameters: ammonium acetate concentration, pH, and percent methanol. The effect of the ammonium acetate concentration demonstrates that the electrolyte is required for efficient ionization and the ESIMS intensity was optimal at a concentration of 2mM for the selected compounds, except 2,4'-dinitrodiphenylamine. The aqueous solution pH, corresponding to the available protons in solution, did not have a significant effect on the ESIMS intensity of the analytes. The percent methanol was evaluated with both decreasing and constant electrolyte concentrations to demonstrate the effects of droplet stability and ion transfer into the gas phase. These findings were applied to the analysis of the selected smokeless powder additives using HPLC-ESIMS to illustrate increased sensitivity for the protonated molecules.