This article explores the relative importance of different socio-demographic and practice-oriented factors that are related to proficiency in Problem Solving in Technology-Rich Environments (PSTRE) and by extension may be related to Complex Problem Solving (CPS). The empirical analysis focuses on the proficiency measurements of PSTRE made available by the Programme for the International Assessment of Adult Competencies (PIAAC), which may be relevant for gaining insight on some of the factors related to CPS. The purpose is to examine the relationship between the broad information processing experience that individuals gather in different contexts over the lifespan, and the chances to develop problem solving skills that adults receive in different sociodemographic profiles. Results reveal that socio-demographic factors such as age, education and immigration status as well as practice-oriented factors such as ICT use and reading practice at and outside work are strongly related to proficiency.