The hosts have the chance to complete a league double over their visitors, who they beat 3-0 in October's reverse fixture.
Benfica were on course to qualify for the last 16 of the Europa League after taking a 2-1 lead on the hour mark against Arsenal, but they conceded twice in the final quarter of the game to lose 3-2.
Back home, Jorge Jesus's men are a long way behind in the title race as they currently trail the league leaders Sporting Lisbon by 15 points with 14 games left to play.
As Aguias are now faced with the task of securing a return to next year's Champions League, and that in itself would take some doing.
The hosts have often had great success on home turf this term, winning seven of their 10 league games to date, while losing just once.
Games against Monday's visitors have been one-sided in recent seasons, with Benfica winning each of the last five meetings by a combined score of 13-5.
Rio Ave's three-game unbeaten run during which they picked up seven points from nine was ended by Famalicao on Sunday in a 1-0 defeat at the Estadio dos Arcos.
The 10 men could not hold out for long as they were breached six minutes before half time by Ruben Vinagre's strike, which ultimately proved to be the decisive moment.
As a result of that loss, the Vilacondenses missed out on the opportunity to move above Santa Clara into eighth place on the log.
Benfica Primeira Liga form: DLDWDD
Benfica form (all competitions): WWDDDL
Rio Ave Primeira Liga form: LLDWWL
Nelson Monte is suspended for the game due to his sending-off last time out, leaving the door open for Ivo Pinto to feature on his return from a calf problem.
Nicolas Otamendi will also serve a one-game suspension here as he picked up his 10th domestic yellow card of the season in Benfica's last league outing.
Diogo Goncalves has made only one league start this campaign but after his excellent performance versus Arsenal, he could keep his place in the starting XI for this one.
Fabio Coentrao is in line to make his comeback from a thigh injury just in time for his side's visit to his former employers.
Benfica possible starting lineup:
Leite; Grimaldo, Vertonghen, Verissimo, Gilberto; Everton, Taarabt, Pizzi, Goncalves; Seferovic, Waldschmidt
Rio Ave possible starting lineup:
Kieszek; Savio, Santos, Borevkovic, Pinto; Geraldes, Pele, Augusto; Mane, Dala, Camacho
We say: Benfica 2-0 Rio Ave
Benfica have had their struggles this season, but they have remained as dangerous as ever on home soil, and we are backing them to claim yet another home win against in a relatively comfortable manner.