Using metals as signal magnified substrates, surface plasmon-enhanced sum frequency generation (SFG) vibrational spectroscopy is a promising technique to probe weak molecular-level signals at surfaces and interfaces. In this study, the vibrational signals of the n-alkane monolayer on the gold (Au) and silica substrates are investigated using the broadband femtosecond SFG. The enhancement factors are discovered to be up to ～1076 and ～31 for the methyl symmetric and asymmetric stretching (ss and as) modes of the monolayer, respectively. By systematically analyzing the second-order nonlinear susceptibility tensor components (χijks), the Fresnel coefficients (Fijks), and the surface plasmon resonance (SPR) effect, we find that the interplay between Fijk and χijk terms and the SPR effect dominate the SFG signal enhancement. Our study reveals that the relative contributions of different influencing factors (i.e., Fresnel coefficients and SPR) to the SFG signal enhancement provide an approach to interpreting enhanced SFG vibrational signals detected from probe molecules on distinct substrates and may finally guide the design of the experimental methodology to improve the detection sensitivity and signal-to-noise ratio.