Molecular vibrations and their dynamics are of outstanding importance for electronic and thermal transport in nanoscale devices as well as for molecular catalysis. The vibrational dynamics of <100 molecules are studied through three-color time-resolved coherent anti-Stokes Raman spectroscopy using plasmonic nanoantennas. This isolates molecular signals from four-wave mixing (FWM) while using exceptionally low nanowatt powers to avoid molecular damage via single-photon lock-in detection. FWM is found to be strongly suppressed in nanometer-wide plasmonic gaps compared to plasmonic nanoparticles. Simultaneous time-resolved incoherent anti-Stokes Raman spectroscopy allows us to separate the contributions of vibrational population decay (T1) and dephasing (T2). With increasing illumination intensity, the ultrafast vibrational dephasing rates of biphenyl-4-thiol molecules are accelerated at least tenfold, while phonon population decay rates remain constant. The extreme plasmonic field enhancement within nanogaps opens up prospects for measuring single-molecule vibrationally coupled dynamics and diverse molecular optomechanics phenomena. Published by the American Physical Society 2024