The article highlights the key socio-psychological factors of formation of healthcare personnel readiness for volunteering. The following features are emphasized on among the basic attributes of volunteering: altruistic, creative, innovative nature of activity implemented in conditions of uncertainty, volatility, various subjective and objective contradictions; diverse activities at various levels of management hierarchy; the explicit prognostic nature of the tasks to be performed; the defining role of the communicative function and the ability to work as part of a team; permanent psychological tension related to considerable responsibility for the decisions made. In this article the readiness is considered from the competence approach perspective. The personal competencies i.e., motivational (individual pursuit of self-actualization, focus on self-realization, the desire to meet the demands of society, orientation to success); intellectual (cognitive and metacognitive); communicative (general speech competence, dialogic competence, interactive competence, narrative competence); personal (self-determination, autonomy, responsibility, independence, managerial qualities, etc.) are the fundamental structural and substantive components of the socio-psychological readiness of healthcare personnel for volunteering. A diagnostic procedure was developed and the socio-psychological readiness for volunteering of healthcare personnel and healthcare system managers, who have certain experience of participating in the volunteer movement, was empirically investigated.