Rotational constants and centrifugal distortion constants of a molecule are the essence of its rotational or rovibrational spectrum (e.g., from microwave, millimeter wave, and infrared experiments). These parameters condense the spectroscopic characteristics of a molecule and, thus, are a valuable resource in terms of presenting and communicating spectroscopic observations. While spectroscopic parameters are obtained from experimental spectra by fitting an effective rovibrational Hamiltonian to transition frequencies, the ab initio calculation of these parameters is usually done within vibrational perturbation theory. In the present work, we investigate an approach related to the experimental fitting procedure, but relying solely on ab initio data obtained from variational calculations, i.e., we perform a nonlinear least squares fit of Watson’s A- and S-reduced rotation–vibration Hamiltonian to rovibrational state energies (resp. transition frequencies) from rotational–vibrational configuration interaction calculations. We include up to sextic centrifugal distortion constants. By relying on an educated guess of spectroscopic parameters from vibrational configuration interaction and vibrational perturbation theory, the fitting procedure is very efficient. We observe excellent agreement with experimentally derived parameters.