A series of low-cost, pyridinium cation-based hypergolic ionic liquids (HIL) containing amine, butyl, or allyl substituents with cyanoborohydride [BH3CN](-) and dicyanamide [DCA](-) anions were developed and characterized. The investigated physicochemical properties include melting and decomposition temperature, viscosity, density, heat of formation (H-f) and specific impulse (I-sp). The ignition delay (ID) of all HILs was tested with the oxidizer RFNA. The HIL, 1-allyl 4-amino pyridinium dicyanamide, exhibited highest density (1.139gcm(-3)) amongst the known pyridinium HILs. The heats of formation predicted on the basis of Gaussian 09 suit programs were within the range of -30 to 356kJmol(-1). The structure of HIL, 1-butyl 4-aminopyridinium cyanoborohydride, was examined by single-crystal X-ray diffraction, which revealed hydrogen bonding between anion and cation as N1-H1NN3=2.07 angstrom, N1-H2NH1B1=2.18 angstrom, and N1-H2NH2B1=2.21 angstrom, respectively. HIL (1-allyl 4-aminopyridiniun cyanoborohydride) exhibited highest I-sp of 228s amongst the designed series.