The psychological well-being of adolescents depends on diverse contextual factors, in particular those relating to the educational and cultural capital of families. The study examined the relationships between psychological well-being of high-ability adolescents, family educational capital, and their school trajectory. The participants were 101 students from 1st year of a public high school in Morelos, Mexico, previously identify by their high intellectual ability. They completed an ad hoc form with information about cultural and academic aspects, and the Spanish version of the Ryff’s Psychological Well-Being Scale. Results shown that the School trajectory factor only had significant effects on Control environment and Purpose in life’s dimensions. Meanwhile the analysis of variances yielded that Cultural capital showed significant differences with the following well-being scales: General, Self-acceptance, Positive relations, and Purpose in life. Furthermore, the interaction between Sex and Cultural capital had only significant effects on Positive Relations and Environmental control favoring men over women, while the interaction of Cultural capital and School trajectory had significant effects only on Purpose in Life dimension. The results emphasize the need for studies that clarify the role of sociocultural context factors in understanding the comprehensive development of highly able adolescents and their psychological well-being.