Methoxyphenols (MP) are a significant component of biomass burning emissions which mainly exists in our atmosphere in the gas phase where they contribute to the formation of secondary organic aerosols (SOA). Rovibrational spectroscopy is a promising tool to monitor atmospheric MPs and infer their role in SOAs formation. In this study, we bring a new perspective on the rovibrational analysis of MP isomers by taking advantage of two complementary devices combining jet-cooled environments and absorption spectroscopy: the JET-AILES and the SPIRALES setups. Based on Q-branches frequency positions measured in the Jet-AILES FTIR spectra and guided by quantum chemistry calculations, we propose an extended vibrational and conformational analysis of the different MP isomers in their fingerprint region. Some modes such as far-IR out-of-plane -OH bending or mid-IR in-plane -CH bending allow to assign individually all the stable conformers. Finally, using the SPIRALES setup with three different EC-QCL sources centered on the 930–990 cm−1 and the 1580–1690 cm−1 ranges, it was possible to proceed to the rovibrational analysis of the ν18 ring in-plane bending mode of the MP meta isomer providing a set of reliable excited state parameters which confirms the correct assignment of two conformers. Interestingly, the observation of broad Q branches without visible P- and R-branches in the region of the C–C ring stretching bands was interpreted as being probably due to a vibrational perturbation. These results highlight the complementarity of broadband FTIR and narrowband laser spectroscopic techniques to reveal the vibrational conformational signatures of atmospheric compounds over a large infrared spectral range.