Research suggests positions of brokerage in organizational networks provide many benefits, but studies tend to assume everyone is equally able to perceive and willing to act on brokerage opportunities. Here we challenge these assumptions in a direct investigation of whether people can perceive brokerage opportunities and are willing to broker. We propose that the psychological experience of power diminishes individuals’ ability to perceive opportunities to broker between people who are not directly connected in their networks, yet enhances their willingness to broker. In Study 1, we find that employees in a marketing and media agency who had a high sense of power were likely to see fewer brokerage opportunities in their advice networks. In Study 2, we provide causal evidence for this claim in an experiment where the psychological experience of power is manipulated. Those who felt powerful, relative to those who felt little power, tended to see fewer brokerage opportunities than actually existed, yet were more willing to broker, irrespective of whether there was a brokerage opportunity present. Collectively, these findings present a paradox of agency: Individuals who experience power are likely to underperceive the very brokerage opportunities for which their sense of agency is suited.