Knowledge on the development of burnout among dentists is important for purposes of prevention and intervention. Using a two-wave longitudinal design, this study examined the chronological sequence of the three dimensions of the Maslach Burnout Inventory: emotional exhaustion; depersonalization; and personal accomplishment. Structural Equation Modelling was employed among a representative sample of Dutch dentists to examine the fit of several models proposed in earlier research. The results indicated that a model in which emotional exhaustion precedes depersonalization, which in turn precedes personal accomplishment, shows an adequate fit among dentists. However, an alternative model, in which personal accomplishment precedes emotional exhaustion, had an even better fit. In addition to the test of these a priori models, an ad hoc model was constructed that best fitted the current data. This model indicated emotional exhaustion to precede the development of depersonalization and personal accomplishment independently. Although not univocal, the results showed that emotional exhaustion should not be discarded as an early sign of burnout. This is in line with the view that emotional exhaustion can be considered as the key dimension of burnout.