Analysis of over 2,000 moments of social interaction collected through smartphone-based experience sampling showed that, over a week-long period, people who have experienced negative relations with others (relative to those who have not), interacted with individuals from less-established relationships, perceived less partner responsiveness during interactions (particularly from their established relationship partners), and were more likely to report being alone than engaged in positive communication episodes. People with high negative relations with others also tended to have lower perceptions of affective well-being and relational connection, and greater perceptions of stress-related cognition, during moments of social interaction. Yet, results also indicated that while positive communication appears harder to come by for people with high negative relations with others, these individuals gain outsized benefits from positive interaction when it occurs (e.g., sharper increases in well-being and decreases in stress). This suggests that heightened negative relations with others might lead people to “hyperabsorb” the benefits of positive moments of communication. The results have implications for key perspectives on communication, relational life, and well-being (i.e., affection deprivation, appraisal, implicit vigilance, and resource insufficiency) and suggest potential routes for intervention development for people with difficult relational lives.