The effectiveness of meditation as a tool to recover from stress has already been widely established. However, less is known about the potential psychological mediating and moderating mechanisms affecting its effectiveness. The present study aimed to advance insight in this respect by examining the mediating role of the recovery experiences “relaxation”, “mastery”, and “detachment”, and by studying the moderating role of intrinsic motivation. To this purpose, after completion of a stress-inducing speech preparation task, 100 participants were randomly assigned to either a 15-minute guided imagery meditation exercise or to a 15-minute radio interview on meditation. Subjectively experienced stress and serenity were included as measures of (recovery from) stress. These measures were completed after the speech preparation task and after the meditation exercise/radio interview. Results showed that participants who meditated reported a larger increase in serenity and decrease in subjectively experienced stress than those who listened to the radio fragment. Furthermore, it turned out that this superior effect of meditation could be partly explained by the mediating effects of “relaxation” and “mastery” (but not “detachment”). The recovery effects of meditation were also stronger for participants who were highly intrinsically motivated for this activity. Altogether, results of this study provide insight into the underlying mediating and moderating mechanisms that explain the effectiveness of meditation as a recovery activity.