[2] His native language is Setswana;[1] his father belonged to the Barolong ba Rapulane of Thaba Nchu in the former Orange Free State but had moved to Johannesburg in his 20s.

[2] In that capacity, he became a friend and colleague of Peter Mokaba, his counterpart in the Mankweng Youth Congress; they were arrested together for their COSAS activities and detained at Johannesburg Prison (Sun City).

[2] Molekane left Parliament after the 1999 general election and joined the Department of Foreign Affairs, first as Consul-General to Bavaria and Baden-Württemberg in Germany from 1999 to 2003.

[1] He later served as High Commissioner to Ghana from 2004 to 2008 and as Ambassador to France from 2014 to 2019, with his ambassadorial terms punctuated by stints at the Department of Foreign Affairs, including on the African Union, Middle East, and Europe desks.

[1] On 10 July 2019, he presented his credentials as Ambassador to Austria;[7] he also has non-resident accreditation to Slovenia and Slovakia and represents South Africa at international organisations based in Vienna.