To what extent can humans form social relationships with robots? In the present study, we combined functional neuroimaging with a robot socialising intervention to probe the flexibility of empathy, a core component of social relationships, toward robots. Twenty- six individuals underwent identical fMRI sessions before and after being issued a social robot to take home and interact with over the course of a week. While undergoing fMRI, participants observed videos of a human actor or a robot experiencing pain or pleasure in response to electrical stimulation. Repetition suppression of activity in the pain network, a collection of brain regions associated with empathy and emotional responding, was measured to test whether socialising with a social robot leads to greater overlap in neural mechanisms when observing human and robotic agents experiencing pain or pleasure. In contrast to our hypothesis, functional region-of-interest analyses revealed no change in neural overlap for agents after the socialising intervention. Similarly, no increase in activation when observing a robot experiencing pain emerged post-socialising. Whole-brain analysis showed that, before the socialising intervention, superior parietal and early visual regions are sensitive to novel agents, while after socialising, medial temporal regions show agent sensitivity. A region of the inferior parietal lobule was sensitive to novel emotions, but only during the pre-socialising scan session. Together, these findings suggest that a short socialisation intervention with a social robot does not lead to discernible differences in empathy toward the robot, as measured by behavioural or brain responses. We discuss the extent to which longer term socialisation with robots might shape social cognitive processes and ultimately our relationships with these machines.