Unless Belarus can avoid defeat against group leaders Kazakhstan in Astana earlier in the day, both teams will be fighting for second spot.
Match preview
Having been relegated from Europe's second tier after only picking up four points from a group containing Czech Republic, Scotland and Israel, many people would have expected the Falcons to bounce back from League C at the first attempt.
However, despite beating Belarus and Azerbaijan both 1-0 away from home, two defeats to Kazakhstan have left them relying on favours from elsewhere if they are to finish first in their group.
With Kazakhstan's match against Belarus set to finish a few hours prior to Slovakia's game against Azerbaijan kicking-off at the Anton Malatinsky Stadium, head coach Francesco Calzona will know his side's ceiling in terms of the Nations League this time around.
Either way, having only been appointed in his first head coach role last month, the 53-year-old will be keen to make a positive impression in his first two matches in charge against nations that his predecessor managed to beat.
For Azerbaijan, who are 128th in the FIFA World Rankings, maintaining their status in Europe's third tier for a second successive Nations League campaign would represent a solid achievement.
Having been promoted from the bottom league in the first instalment of the competition, the Caucasus-based country finished third last time around, which is the position that they find themselves in ahead of their trip to Slovakia this week.
Indeed, their win against Belarus last time out moved them two points above their opponents and off the foot of Group 3 in the process. With Belarus facing two tricky away games in the forthcoming week, head coach Gianni De Basi may be confident that his side's primary objective is already close to being achieved.
However, the former Torino boss will not allow his players to be complacent, especially with so much still to be played for. Whether first or second spots are still open ahead of kickoff in Trnava on Thursday, maximum effort and organisation will be required from his team if they are to inflict a shock result against their more illustrious opponents.
Slovakia Nations League form:
Slovakia form (all competitions):
Azerbaijan Nations League form:
Azerbaijan form (all competitions):
Team News
Slovakia should welcome Milan Skriniar back to the fold after the Inter Milan defender was not included in his national team's previous squad in June due to a hamstring injury.
Following the international retirement of Marek Hamsik, the 27-year-old is expected to be named Slovakia's permanent captain ahead of Thursday's match, with Calzona revealing in his press conference, "I'm going to immediately ask the players who they want. If they say Skriniar, I will agree."
One senior player who will not be available for selection is Ondrej Duda, who is suspended for after his red card in the defeat to Kazakhstan, while Lukas Haraslin is a doubt due to a knee injury.
Azerbaijan, meanwhile, are also missing a player through suspension, with Qismat Aliyev serving one more match on the sidelines after his dismissal in a 0-0 draw against Belarus earlier in the competition.
De Basi is likely to stick with the same starting XI which ended a winless run of 12 matches by beating Belarus last time out.
Slovakia possible starting lineup:
Rodak; Pekarik, Gyomber, Skriniar, Hancko, De Marco; Kucka, Lobotka, Hrosovsky; Jirka, Bozenik
Azerbaijan possible starting lineup:
Mehemmedeliyev; C Huseynov, Mustafazada, Guseynov; A Huseynov, Makhmudov, Pascual, Almeida, Salahli; Dadashov, Sheydayev
We say: Slovakia 2-0 Azerbaijan
Slovakia's players are likely to be more motivated than usual given that they are playing in front of their new manager for the first time.
Azerbaijan are rarely thrashed, but they are regularly beaten, and we can not envisage much else in Trnava on Thursday.