The present study investigated whether cortisol stress responses of 6-year-olds were associated with their behavioral functioning at school. Additionally, the moderating role of stress in the family environment was examined. To this end, 149 healthy children (M-age = 6.09 years; 70 girls) participated in an age-appropriate innovative social evaluative stress test. Saliva cortisol samples were collected six times during the stress test to calculate two indices of the cortisol stress response: cortisol stress reactivity and total stress cortisol. Teachers assessed children's internalizing, externalizing, and prosocial behaviors. Stress in the family environment was operationalized as maternally reported parenting stress. Results indicated a significant increase in cortisol concentrations in response to the stressor. No significant associations were found between cortisol stress responses and behavioral functioning at school and there was no evidence for moderation by maternal parenting stress. Potential theoretical and methodological explanations for these results are discussed.