Moderator of its governing body the General Assembly, Rt Rev Dr Derek Browning (pictured above, sitting) signed the Armed Forces Covenant at Edinburgh Castle last night.
The Covenant states: "We recognise the value serving personnel, regular and reservists, veterans and military families contribute to our organisation and our country.
"Therefore we, the General Assembly of the Church of Scotland, will endeavour in our business and charitable dealings to uphold the key principles of the Armed Forces Covenant."
The Church has pledged to support employees who are veterans and "look favourably" upon staff requests for leave and flexible working by spouses with partners on deployment and compassionate leave.
Six per cent of Scotland's population has served in the Armed Force. Including their families, the Armed Forces Community represents nearly one in ten people.
Gordon Craig, convener of the Church of Scotland Committee on Chaplains to HM Forces said: "The wording of the Covenant will allow the Kirk to demonstrate its support of this group of people pastorally, liturgically and organisationally."
Under the document, presbyteries will appoint Veterans' Champions who will support parish ministers in signposting people to appropriate care.
Church of Scotland ministers will be encouraged to learn more about local military bases, reserve centres and Cadet training facilities.
The Armed Forces Covenant has already been signed by more than 1,500 organisations across the UK, including the Church of England.
The Church of Scotland's signing of the Armed Forces Covenant coincided with Armed Forces Day 2017, which saw events held across the country.