Positive affect is associated with longevity and favourable physiological function. We tested the hypothesis that positive affect is related to health-protective psychosocial characteristics independently of negative affect and socio-economic status. Both positive and negative affect were measured by aggregating momentary samples collected repeatedly over 1 day, and health-related psychosocial factors were assessed by questionnaire in a sample of 716 men and women aged 58–72 years. Positive affect was associated with greater social connectedness, emotional and practical support, optimism and adaptive coping responses, and lower depression, independently of age, gender, household income, paid employment, smoking status, and negative affect. Negative affect was independently associated with negative relationships, greater exposure to chronic stress, depressed mood, pessimism, and avoidant coping. Positive affect may be beneficial for health outcomes in part because it is a component of a profile of protective psychosocial characteristics.