Casemiro played 120 minutes for Tite’s side, and scored from the spot, but his effort proved to be in vain for the South Americans.
Fellow Reds Antony and Fred were introduced from the bench in the encounter at the Education City Stadium in Al Rayyan, which was poised at 0-0 for the majority, before goals for either side in extra-time took it to a shootout.
United defender Alex Telles, on loan at Sevilla, watched on from afar after picking up a tournament-ending injury earlier in the campaign, as Brazil bowed out in heartbreaking fashion.
Reds midfielder Casemiro was involved in an intriguing tactical contest from the off, with Croatia not allowing Brazil to possess the dominance that they had in their last-16 win over South Korea, earlier in the week.