Background: The objectives of the study were to explore a self-report measure for psychological well-being and to investigate the relationship between psychological well-being and psychological distress. Method: Telephone interviews of a representative sample of adults (N = 1933) collected information about sociodemographic variables, a standardised measure of psychological distress, and three brief existing scales to assess aspects of psychological well-being: Positive Relations with Others, Environmental Mastery, and Satisfaction with Life. The total of these three scales was also computed and explored as a measure of overall well-being. Results: Variables positively associated with psychological well-being were negatively associated with psychological distress and vice versa. For example low psychological well-being and high psychological distress were associated with being the only adult in the household, speaking a language other than English at home, being divorced or separated, having no educational qualifications beyond secondary school, being unable to work, having a low income, renting one's accommodation, and receiving a pension. Conclusions: The measure of well-being shows psychometric promise for community surveys. Psychological well-being is not exactly the opposite end of the continuum to psychological distress, but more debate is needed about whether and when, research participants need to be asked questions about both.