Volunteers fill a large variety of important roles in society, roles which differ substantially depending on the nature of the job. The majority of current literature focuses on the personality traits and motivations that serve to distinguish volunteers as a whole from the general population. Acknowledging this, the present study examines differences within the volunteer population, comparing two volunteer groups with roles deemed either high or low personal risk, on measures of a five factor model of personality, sensation seeking and functional motivation to volunteer. Univariate differences were found between the groups on all three measures. Multivariate analysis showed Emotional Stability, SS-Disinhibition, and the Social, Values and Understanding motivations to be significant predictors of specific volunteer group membership. Results are discussed in relation to the adequacy of using one volunteer function scale to assess the diverse range of volunteer roles and as to the potential fulfilment of sensation seeking arousal through volunteering.