In the semi-finals, Brazil suffered a 7-1 humiliation at home by eventual winners Germany - with Luiz bearing the brunt of the blame for the result.
For Brazilian football, the match has gone down in infamy. It's been dubbed the 'Mineirazo', or the 'Agony of Mineiro', with the humiliation staged at the Estadio Mineiro in Belo Horizonte.
The result also evoked a "spirit of national shame" known as the 'Maracanazo' in reference to when Brazil unexpectedly lost the 1950 World Cup on home soil to Uruguay.
For Luiz and his Selecao teammates, things didn't get better for the third-place playoff, with Brazil losing 3-0 to Holland.
Asked about the experience, Luiz admits he was left feeling abandoned as apart from him, none of the players at the time spoke up.
“We were not used to losing by two, three goals difference. Suddenly it was a blow. A game in which everything goes wrong. Today I think about it and, maybe at that moment, as captain, with 3-0 I go and say 'wait, stop everyone, come here'. We go to rest, we come back, we score a goal and everything changes. But to have that preparation you need to live it and I had not lived that before."
Reflecting on the aftermath, Luiz knows the hurt still lingers for the football mad nation.
Luiz added: “I apologise to everyone, to the Brazilian people. Everyone knows how important it was to me, to the group. I just wanted to give my people a joy, my people, who suffered so much. It is a day of great sadness."
- updated May 25