We propose and demonstrate pump-probe spectroscopy of rubidium absorption that reveals the sub-Doppler hyperfine structure of the ${}^{5}{\mathrm{S}}_{1/2}\ensuremath{\leftrightarrow}{}^{5}{\mathrm{P}}_{3/2}$ (
D2) transitions. The counterpropagating pump and probe lasers are independently tunable in frequency, with the probe operating at the single-photon level. The two-dimensional spectrum measured as the laser frequencies are scanned shows fluorescence, Doppler-broadened absorption dips, and sub-Doppler features. The detuning between the pump and probe lasers allows compensation of the Doppler shift for all atomic velocities in the room-temperature vapor, meaning we observe sub-Doppler features for all atoms in the beam. We detail a theoretical model of the system that incorporates fluorescence, saturation effects, and optical pumping and compare this with the measured spectrum, finding a mean absolute percentage error of 3.11%. This high level of agreement allows us to extract the number density and temperature of the
Rb vapor from the two-dimensional spectrum. In the future this technique could be used as an atomic frequency standard for calibrating and characterising a single-photon or low-light-level source.