<jats:p>The difficulty in achieving high spectral resolution and accurate line shape in sum-frequency generation vibrational spectroscopy (SFG-VS) has restricted its use in applications requiring precise detection and quantitative analysis. Recently, the development of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution generated by synchronizing two independent amplifier lasers have opened new opportunities for probing an intrinsic SFG response. Here, we present a new flexible approach to achieve HR-BB-SFG-VS. In this system, two regeneration amplifiers shared the same oscillator laser as the seed, and a time-asymmetric visible pulse with a nearly Lorentzian line shape filtered by an etalon was used to overlap with a femtosecond broadband infrared pulse. This Lorentzian line shape of the visible pulse can greatly simplify the spectral fitting and analysis. We also demonstrated that the single-sided long visible pulse provided both high spectral resolution (1.4 cm−1) and effective suppression of the non-resonant background by detuning the time delay between visible and infrared pulses in SFG-VS measurements. With this new SFG setup, a pair of spectral splittings by 3.1 ± 0.7 and 3 ± 0.2 cm−1 for the symmetric and antisymmetric stretching of the CH3 group was resolved at the CH3CN/TiO2(110) surface, which are tentatively attributed to two different orientational methyl groups. These technological advancements can help broaden the applications of HR-BB-SFG-VS and provide solid ground for a better understanding of complex molecular structures and dynamics at interfaces.</jats:p>