The intriguing phenomenon of many-body localization (MBL) has attracted significant interest recently, but a complete characterization is still lacking. In this work we introduce the total correlations, a concept from quantum information theory capturing multipartite correlations, to the study of this phenomenon. We demonstrate that the total correlations of the diagonal ensemble provides a meaningful diagnostic tool to pin-down, probe, and better understand the MBL transition and ergodicity breaking in quantum systems. In particular, we show that the total correlations has sublinear dependence on the system size in delocalized, ergodic phases, whereas we find that it scales extensively in the localized phase developing a pronounced peak at the transition. We exemplify the power of our approach by means of an exact diagonalization study of a Heisenberg spin chain in a disordered field. By a finite size scaling analysis of the peak position and crossover point from log to linear scaling we collect evidence that ergodicity is broken before the MBL transition in this model.