The dicarbon molecule, C2, is one of the most important diatomic species in various gaseous environments. Despite extensive spectroscopic studies in the last two centuries, the radiative and photodissociative properties of C2 in its highly excited electronic states are still largely unexplored, particularly in the short vacuum ultraviolet (VUV) region. In this study, the lifetimes of C2 for rotational levels in the recently identified 13Σg+ state up to the vibrational level ν' = 4 and in the f3Σg- state up to ν' = 2 are measured for the first time with a VUV-pump-UV-probe photoionization scheme. It is found that all rovibrational levels in the f3Σg- state have lifetimes shorter than the dynamical limit of ∼4.7 ns of the present method, and the lifetimes in the 13Σg+ state show obvious and complex dependence on the rotational and vibrational quantum levels. Generally, the lifetime in the 13Σg+ state becomes shorter at higher rotational and vibrational levels, i.e., the longest lifetime measured in the ν' = 0 level is ∼18 ns, while all rotational levels in the ν' = 4 level are found to have shorter lifetimes than ∼4.7 ns. This implies that predissociation might occur and become more prominent at the higher energy levels in the 13Σg+ state. The prominent dependence of the lifetime on the rotational, vibrational and electronic level indicates complex dynamical processes in the highly excited states of C2.