We have developed the technique of population-controlled impulsive vibrational spectroscopy (PC-IVS) aimed at providing high-quality, background-free Raman spectra of excited electronic states and their dynamics. Our approach consists of a modified transient absorption experiment using an ultrashort (<10 fs) pump pulse with additional electronic excitation and control pulses. The latter allows for the experimental isolation of excited-state vibrational coherence and, hence, vibrational spectra. We illustrate the capabilities of PC-IVS by reporting the Raman spectra of well-established molecular systems such as the carotenoid astaxanthin and trans-stilbene and present the first excited-state Raman spectra of the retinal protonated Schiff base chromophore in solution. Our approach, illustrated here with impulsive vibrational spectroscopy, is equally applicable to transient and even multidimensional infrared and electronic spectroscopies to experimentally isolate spectroscopic signatures of interest.