Volunteer recruitment and retention continue to be important issues for not-for-profit organisations. A theoretical framework that has demonstrated considerable potential to better understand the factors influencing volunteer recruitment and retention is the concept of the psychological contract (PC); the set of beliefs individuals hold in relation to how organisations value their contributions as volunteers. To date research has predominantly examined the relationship between volunteer retention and individuals’ PC after a volunteer has spent considerable time with an organisation. The research reported in this paper provides evidence that volunteer recruitment practices and volunteer’s expectations directly influence the development of volunteers’ PCs from the very first interactions they have with an organisation, and before they even commence their voluntary duties. The results indicate that a better understanding of volunteers’ PC development processes and the influence of volunteer manager actions during the volunteer recruitment phase can support the formation of realistic expectations amongst potential volunteers and thus enhance volunteer recruitment outcomes.