During his primary school years he attended Escola Particular do Centro Social e Paroquial de Nossa Senhora da Conceição, a period he often mentions as being responsible for some of the most important things he has learned throughout his life, particularly due to his teacher, Aníbal Rocha.

In 1983, while preparing for the diplomatic service concours, he attended the course Cycle d’Histoire du XXeme Siècle at the Abbey of Prémontrés in Pont-à-Mousson, Lorraine, France, organized by the Institut d'études politiques de Paris (commonly known as Sciences Po).

Between 1990 and 1993, in a time coinciding with the aftermath of the fall of the Berlin Wall and the collapse of the Soviet Union, he served as deputy-director to the Cabinet of then Secretary General of NATO, Manfred Wörner.

As Advisor to Deus Pinheiro, one of Luís de Almeida Sampaio's main tasks was to participate in the set up of the first European Commission Conflict Prevention guidelines.

[5] He had the opportunity to develop this concept at an OSCE Seminar held in Sofia, Bulgaria, on “Cooperation among International Organisations and Institutions: Experience and Prospects in South-Eastern Europe” on May 17, 1999:[6] “Mr.

[2] During his post in Luanda, marked by the death of UNITA’s Angolan rebel leader, Jonas Savimbi, and the final days of the Angolan Civil War, Luís de Almeida Sampaio was a member of the Portuguese delegation (comprising the “troika for peace” with the United States of America and Russia) responsible for the signing of the Memorandum of Understanding as an addendum to the Lusaka Protocol.

[2] During this period, more precisely during the 2007 Portuguese presidency of the European Union, he served as coordinator for the Middle East Peace Process (MEPP) in the Israeli-Palestinian conflict.

[11][12] Luís de Almeida Sampaio served as Portuguese ambassador to Germany between 2012 and 2015, having presented his diplomatic credentials to President Joachim Gauck in Berlin on April 13, 2012.