Fourier transform spectroscopy and intracavity laser absorption spectroscopy are used to record the absorption spectrum of formic acid at high spectral resolution, in the ranges of the 2νOH (6968.258 cm−1) and 4νOH (13 284.075 cm−1) vibrational bands of the trans-rotamer, respectively. Numerous perturbations combined with a large line density limit the extent to which the vibration–rotation analysis is performed. Some 689 lines are assigned in the first overtone band and related vibration–rotation constants are determined. Only the band origin and upper state principal A-rotational constant are determined for the n=4 overtone band, because of much higher spectral density. Interpolation, helped by literature data, provides all missing principal rotational constants in the nOH series, for n=1 to 4. All major vibration–rotation parameters appear to evolve very smoothly along the series. This trend is fully supported by ab initio calculations performed at the MP2/cc-pVTZ level of theory and based on an effective one-dimensional model describing the OH local mode stretching vibration. Results of these calculations are detailed in terms of the mean nuclear structure in the excitation series, up to n=4. The related calculated dipole moment surface allows the experimental a:b subband intensity ratio in the series to be interpreted in terms of a decrease in the HOC angle, from Θ≈90° (n=1) to 44°(n=4). The potential occurrence of a proton exchange mechanism between the two oxygen nuclei, close to a tautomerism mechanism, is discussed.