Molecular parameters for the a3Πu and b3Σg− states in C2 (Ballik–Ramsay system) are determined by a nonlinear least squares fit directly to the observed wavelengths. No satellite lines are observed in the electronic spectra of C2, and the influence of nuclear statistics yields further restrictions with regard to observable lines. The present approach, however, yields accurate values of the various triplet splitting and Λ-doubling parameters in spite of this lack of experimental information. Finally a refined value of the triplet–singlet energy separation is obtained.