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Aims and objectives This study examines the impacts of mentor–mentee rapport on willingness to mentor/be mentored, self‐efficacy, outcome expectations, career interest and subsequently on nurses’ professional turnover intention. Background Workplace relationships, whether positive or negative, influence nurse turnover within an organisation. Yet little is known about the effects of mentoring on nurses’ intentions to leave the nursing profession. Design A cross‐sectional, survey‐based research design was used to collect data from a large medical centre in Northern Taiwan. Methods Study concepts were measured using scales from social capital theory (SCT), social cognitive career theory (SCCT) and the nursing literature. Partial least square structural equation modelling was used to test all study hypotheses. The STROBE statement was chosen as the EQUATOR checklist. Results For mentors, rapport was positively related to willingness to mentor, which was positively related to outcome expectations, and further, positively related to career interest and negatively related to professional turnover intention. For mentees, rapport was positively related to willingness to be mentored, which was positively related to self‐efficacy, outcome expectations and ultimately to career interest. Career interest was negatively related to professional turnover intentions. Conclusions Rapport between mentors and mentees may be an important means to retain nurses in the profession. Relevance to clinical practice Managers should consider taking steps to enhance rapport between mentors and mentees. In doing so, managers improve nurse retention, a critical component of providing high‐quality patient care.