We present the results of a long-term high-resolution spectroscopy campaign on the O-type stars in NGC 6231. We revise the spectral classification and multiplicity of these objects and we constrain the fundamental properties of the O-star population. Almost three quarters of the O-type stars in the cluster are members of a binary system. The minimum binary fraction is 0.63, with half the O-type binaries having an orbital period of the order of a few days. The eccentricities of all the short-period binaries are revised downward, and henceforth match a normal period-eccentricity distribution. The mass ratio distribution shows a large preference for O + OB binaries, ruling out the possibility that, in NGC 6231, the companion of an O-type star is randomly drawn from a standard initial mass function. Obtained from a complete and homogeneous population of O-type stars, our conclusions provide interesting observational constraints to be confronted with the formation and early evolution theories of O-stars.