Catherine Johnstone, who has been the interim chief executive of Samaritans since March, has been appointed to the post on a permanent basis.
She was brought in to run the charity after the unexpected resignation of the former chief executive, Dominic Rudd.
Johnstone told Third Sector that her priorities would be the implementation of the charity's six-year strategy, Taking the Lead to Reduce Suicide, and the expansion of its whole range of services.
"We are keen to broaden the services we provide, particularly in terms of local outreach work, alongside more national influencing in the policy arena," she said.
Johnstone has worked in the charity sector for 15 years. Her career has included a stint as interim chief executive of infrastructure quango Capacitybuilders.
Sophie Andrews, chair of Samaritans, said: "Catherine's superb people skills, passion for her job and undeniable commitment to Samaritans have shone out to all who have worked with her over the past few months."