Volunteering has gained considerable attention within society. It is a way to show concern for others, but it can also be loaded with personal and selfish goals. This study looks at the relationship between the Third Sector and volunteering, and seeks to identify the real motivations that lead individuals to engage in voluntary activities. Therefore, the Volunteer Functions Inventory model was used, which collected responses from 130 volunteers, and concluded that among the six profiles proposed, the one related to values, altruism and humanitarianism is the great motivator of individuals in volunteering. Finally, we propose a reflection on the people management process, associated with attracting, recruiting and retaining volunteers, significantly considering the motivational profiles identified, in order to improve voluntary practices and experiences.