This electronic momentary assessment study explored the relationship between flow and pain intensity and examined whether flow is an optimal experience for people with chronic pain. Adults with chronic pain (n = 30) were signaled randomly seven times daily during 1 week to respond to a flow questionnaire via personal digital assistant. The participants responded to 718 questionnaires from 1,447 beeps (response rate = 49.6%). Results indicated that participants were most commonly at home, doing self-care activities, with family or alone. Participants experienced flow 34.9%, apathy 44.6%, relaxation 11.6%, and anxiety 8.9% of the sampled time. Participants' mean concentration, self-esteem, motivation, and potency scores were highest in flow compared to the other three states. Separate one-way between-groups analyses of variance comparing concentration (F(3) = 11.85; p < .001), self-esteem (F(3) = 11.98; p < .001), motivation (F(3) = 29.29; p < .001), positive affect (F(3) = 2.89; p = .035), potency (F(3) = 19.88; p < .001), and pain intensity (F(3) = 1.39; p = .245) scores across the four states showed a significant overall effect on all comparisons except pain intensity and positive affect.