Optical-optical double resonance (OODR) spectroscopy is a powerful tool for the experimental assignment of highly-excited molecular states, which in turn is needed for verification of the accuracy of theoretical predictions of high-temperature spectra observed in exoplanets and in combustion environments. Previous implementations of OODR used either continuous wave (cw) lasers, which limit the number of transitions that can be detected, or pulsed lasers, which limit the spectral resolution. Recently, we demonstrated OODR with a cw pump and a frequency comb probe and applied it to the detection and assignment of methane transitions in the 3ν 3 ← ν 3 range with sub-Doppler resolution over 200 cm -1 of bandwidth [1]. The pump [see Fig. 1(a) ] was a 1 W 3.3m idler of a cw optical parametric oscillator (cw-OPO), stabilized to the Lamb dip in a selected CH 4 transition in the ν 3 band using a signal from a reference cell. The probe was an amplified fully-stabilized Er:fiber comb ( f rep = 250 MHz), whose center wavelength was shifted to 1.67m using a soliton self-frequency shift fiber (SSSF). The sample of pure CH 4 was contained in an 80-cm-long single-pass cell cooled by liquid nitrogen. The probe spectra were detected using a Fourier transform spectrometer (FTS) with comb-mode-limited resolution [2] , and the final interleaved spectra had 2 MHz sampling point spacing. Figure 1(b) shows the 3ν 3 ← ν 3 R(1) transition at 6046.36008(5) cm -1 , detected with the pump on the ν 3 R(0) line. We measured, fit and assigned 36 probe transitions with the pump tuned to 9 different transitions. Figure 1(d) shows a comparison of the probe transition wavenumbers to predictions from the TheoReTS database [3] , demonstrating agreement within 1 cm -1. © 2021 IEEE.