Diego Simeone's side are second in the table, four points behind the leaders Barcelona, while Rayo occupy ninth position, picking up seven points from their opening five games of the season.
Match preview
Rayo picked up four points from their opening two league matches of the season, beating Real Sociedad 2-1 before drawing 0-0 with Getafe, but they then lost back-to-back games to Barcelona and Espanyol.
The capital outfit managed to return to winning ways against Osasuna on Monday night, coming from behind to record a 3-1 victory, with the result moving them onto seven points, which is enough for ninth spot.
Inigo Perez's side finished 17th in La Liga last season, avoiding relegation by just five points, and they are now playing in their fourth straight campaign at this level of football.
Rayo have lost each of their last three league games against Atletico, while they have not managed to overcome the Red and Whited since February 2013, which is an indication of the size of their task in this match.
Last season, Atletico did a league double over Rayo, including a 7-0 victory in the corresponding fixture, but the reverse game at Wanda Metropolitano was much closer, with the hosts winning 2-1.
Atletico, meanwhile, have been in strong form early in the season, picking up 11 points from their five La Liga matches courtesy of a record of three wins and two losses, and they sit second in the table.
Simeone's team are currently four points behind division leaders Barcelona and level on points with Real Madrid and Villarreal in third and fourth respectively, so a lot could change in a short space of time.
Atletico drew their La Liga opener against Villarreal before recording a 3-0 victory over Girona, but they were then held at home by Espanyol in their third match of the campaign.
The Red and Whites have managed to win their last two in the league, beating Athletic Bilbao 1-0 before the international break, which was followed by a 3-0 success over Valencia last weekend.
Atletico will also enter this match off the back of a Champions League win, beating RB Leipzig 2-1 in the competition on Thursday evening, meaning that the capital team will be bidding to make it four straight wins when they take to the field on Sunday night.
Rayo Vallecano La Liga form:
Atletico Madrid La Liga form:
Atletico Madrid form (all competitions):
D
W
D
W
W
W
Team News
Rayo remain without the services of Alfonso Espino and Diego Mendez for this match, but the home side are otherwise in strong shape ahead of their contest with Atletico.
Head coach Perez could make a couple of changes to the side that started against Osasuna, with Isi Palazon and Unai Lopez potentially being introduced into the side.
Lopez netted off the bench against Osasuna, while Palazon made a strong impact as a second-half substitute, with the pair now in line for starts, but Sergio Camello should continue through the middle.
As for Atletico, Pablo Barrios is out with a muscular problem, but the capital side have not reported any fresh concerns from their Champions League game against Leipzig.
There will be changes from the side that started the European encounter, with Samuel Lino, Conor Gallagher and Alexander Sorloth expected to return to the side.
Angel Correa, Rodrigo De Paul and Rodrigo Riquelme could be the three players to drop down to the bench, with Antoine Griezmann set to feature off the back of an excellent performance in the Champions League.
Rayo Vallecano possible starting lineup:
Batalla; Ratiu, Lejeune, Mumin, Chavarria; Valentin, Trejo, U Lopez; Palazon, Camello, A Garcia
Atletico Madrid possible starting lineup:
Oblak; Le Normand, Gimenez, Reinildo; Llorente, Gallagher, Koke, Lino; Alvarez, Sorloth, Griezmann
We say: Rayo Vallecano 1-2 Atletico Madrid
Atletico have so much quality all across the pitch, and with Simeone having the luxury of freshening his side this weekend, we are not expecting a European hangover. Rayo have enough quality to score, but we are backing the visitors to navigate their way to all three points on Sunday night.