Estimation of children’s chronological age is highly important in human and forensic sciences. The Demirjian method has been reported as accurate for this purpose. The literature review shows some evidence that the accuracy of estimating chronological age via the Demirjian standards is not a straightforward process. The objective of this research is to analyze the reliability of the Demirjian standards in Portuguese and Spanish children and adolescents and adapt it to include sex and group age as contingent factors. Methods: Orthopantomographs of 574 Portuguese and Spanish male and female children and adolescents were employed to test the reliability of the Demirjian method. After testing for inter-rater consistency and age estimation using the Demirjian standards, multiple regression analysis was performed controlling for sex and age group. Results: The Demirjian standards overestimated chronological age for both sexes, mainly for females. Through the development of regression functions, more detailed dental age estimation was performed. The predictive capacities of the Demirjian method and the significant teeth varied as a function of children’s age. The Demirjian global standard predicted over 65% of the variance of the chronological age. Taking a tooth-by-tooth approach, the predictive ability increased by over 70%. Conclusions: The accuracy of estimating chronological age via the Demirjian method is not as reliable as it might appear, judging from the results found according to age group and according to sex crossed with age group.