The Scots have the chance to win their sixth international match in a row, while Slovakia are still searching for their first win in League B Group 2.
It was a historic night at Hampden Park on Thursday evening as Scotland qualified for their first major tournament since 1998 after beating Serbia on penalties following a 1-1 draw in 90 minutes.
After Ryan Christie opened the scoring seven minutes into the second half, the Scots looked to be holding on for a narrow victory, however Luka Jovic's header in the 90th minute took the match to extra time.
With no further goals, the match went to penalties and after Scotland had scored all five of their spot kicks, David Marshall saved Aleksandar Mitrovic's effort from 12 yards to secure Scotland's place at Euro 2020.
Scotland, who have extended their unbeaten run to nine matches in all competitions, will now face England at Euro 2020, along with Croatia and the Czech Republic in Group D.
Manager Steve Clarke now turns his attention to the Nations League where they face Slovakia for the second time, after previously beating them 1-0 last month.
A win for the Scots could see them extend their lead at the top of League B Group 2 to seven points.
Thursday was also a memorable night for Slovakia as they beat Northern Ireland 2-1 after extra time to secure their place at Euro 2020.
The Repre however have had little success in the Nations League this campaign, having failed to win any of their four matches in League B Group 2, with Stefan Tarkovic's men facing relegation to League C as things stand.
Slovakia were hit hard by coronavirus last month but should have a stronger squad this time around. A win against Scotland would see them remain bottom of the group, while narrowing the gap on third place to one point.
Slovakia Nations League form: LDLL
Slovakia form (all competitions): LDWLLW
Scotland Nations League form: DWWW
Scotland form (all competitions): DWWWWW
Slovakia have started six different players at left-back in their last seven internationals and with experienced full-back Tomas Hubocan starting against Northern Ireland, Robert Mazan may be handed a place in the starting XI on Sunday.
Slovakia possible starting lineup:
Rodak; Pekarik, Gyomber, Skriniar, Mazan; Kucha, Lobotka, Hamsik; Mak, Duda, Rusnak
Scotland possible starting lineup:
Marshall; McTominay, McKenna, Tierney; O'Donnell, McLean, McGinn, McGregor, Robertson; Christie, Dykes
We say: Slovakia 1-1 Scotland
Scotland have won their last two matches 1-0 against Sunday's opponents, but with Slovakia having a stronger side to field this time around, we expect the hosts to secure a point at the Anton Malatinsky Stadium.