Psychological well-being in adolescence is an increasing field of study. Deepening in its knowledge during this period of life can be of a lot of help to the designing of more adjusted prevention programs aimed to avoid or reduce the problems adolescents might be experiencing. Complexity theories can be a productive alternative to the important limitations explanations about psychological well-being in adolescence have nowadays. Answers to a questionnaire have been obtained from a sample of 968 Catalan adolescents from 12 to 16 years old including 29 psychological well-being indicators measuring 8 dimensions related to satisfaction with specific life domains, self-esteem, perceived social support, perception of control and values. A structural equation modelling approach to complexity that focuses on the non-linearity property has been followed. Given the large number of dimensions, the model has been estimated in two steps. First, a confirmatory factor analysis model has been fitted to the 29 indicators and appropriate factor scores have been saved. Then all possible products and squared terms of the factor scores have been computed and have been used as predictors of the dependent variable using an ordered logit model. The results show that a non-linear model including interaction effects among the 8 dimensions, age and gender, has a higher explanatory power to predict satisfaction with life as a whole, compared to a linear model estimated from those same indicators. This work must be understood as a first step, basically a methodological one, to the future elaboration of new models of psychological well-being in adolescence to be based on the principles defended by complexity theories.