According to the psychological flexibility model, “we hurt where we care, and we care where we hurt.” This suggests that values-based living and hedonic well-being are not always positively correlated, such as when engaging in valued action in the presence of important but stressful situations, which may reduce joy or increase sadness. Despite this prediction, past studies have focused on the average effects of valued living on hedonic well-being and found positive associations. In order to examine the heterogeneity of the within-person links of values-based action with hedonic well-being and the possibility of negative associations, we used intensive experience sampling methods (participants (n) = 425; 71.76% female; age = M(SD) = 22.20 (6.85); sampling design: 3-4 prompts per day; total measurements (n) = 6,456). Time series and meta-analytic models revealed that increases in values-based living were positively related to hedonic well-being, but the heterogeneity in this effect was so great (I2 > .80) that the average estimate did not apply to many people. Indeed, for some, valued action was associated with little joy and/or much sadness. A variety of aggregation methods based on idiographic models were examined. A sub-group was identified, which we labeled the ‘Stoics,’ for whom engagement in valued action in daily life was not contingent on sadness or joyfulness, unlike the Non-Stoics, as revealed in within-person networks. While overall levels of affect, valued action, and stressful events were the same in the two groups, network analysis further revealed that for Stoics, stressful situations were linked to valued action, but not hedonic well-being. For Non-Stoics, valued action was less likely in stressful situations, but when valued action did occur it was associated with more joy and less sadness. We discuss the implications of these results for personalizing interventions.