Clarification of personal values and meditation practice has been associated in most meditation traditions and in academic texts. Both values-related behavior and meditation practice increases well-being, but their relationship has not been well studied. It has been suggested that values, together with self-regulation, psychological flexibility, and exposure, are key mechanisms of action in mindfulness. The aims of this study were to explore the association between meditation and values and to examine the processes involved in this relation. A sample of 235 meditation-naïve participants and 274 subjects with varying levels of experience in meditation practice completed an online assessment protocol composed of Five Facets of Mindfulness Questionnaire (FFMQ), Decentering Questionnaire (EQ), Valued Living Questionnaire (VLQ), and Engagement with Life Scale (ELS). Results revealed that daily meditators were more consistent, aware, and life-fulfilled about their values; moreover, these measures correlated with the mindfulness process and decentering. The relation between meditation practice and values-related behavior (assessed by the VLQ) was mediated by decentering. The association between meditation practice and Valued Living and Life Fulfillment (measured by the ELS) was mediated by the decentering, describing, and nonjudging dimensions of mindfulness. The findings in this study support the relation between meditation and personal values, mediated by the decentering, describing, and non-judging facets of mindfulness.