(1) Background: Trial of labor after cesarean (TOLAC) can be associated with significant maternal and neonatal complications, and the aim of this retrospective study was to calculate the risks and probabilities of these complications in two tertiary maternity centers in Romania. (2) Methods: A total of 216 patients who attempted TOLAC were included in the study and were segregated into two groups, depending on TOLAC success. Medical records were assessed, and clinical data were used to determine the maternal and neonatal risks and complications, using multinomial logistic regression and postestimation predictions. (3) Results: Our data indicated that patients who had a failed TOLAC had significantly higher risks and probabilities of uterine rupture, either complete or incomplete; intensive care unit (ICU) admission; and emergency hysterectomy. The newborns of these mothers had significantly higher risks and probabilities of low Apgar score at birth, neonatal intensive care unit (NICU) admission, and invasive ventilation. (4) Conclusions: Failed TOLAC could lead to significant maternal and neonatal complications, and women who attempt this procedure should be monitored in a tertiary center where a multidisciplinary team and an emergency operating room are available.