The hosts will aim to break a six-year absence from the top flight, having suffered a relegation to the Segunda Liga in 2015, while Rio Ave have not featured in the second tier since they achieved promotion in 2008.
Arouca put together an eye-catching run of nine consecutive wins at the end of the season to finish in third spot, an especially impressive charge considering they only ended three points above fourth-placed Academica.
They sealed the third-placed finish with a 3-1 home victory over sixth-placed Chaves on the final day, as a Pite brace won the game after Olavio Vieira scored for the visitors to cancel out Andre Silva's opener.
Their solid run in the final two months of the season meant that Quim Machado's side managed to overtake and then fend off Academica, booking their place in the playoff as they aim to return to the top flight.
If they are to do so, Os Arouquenses will feature in the Primeira Liga for the first time since 2015, as they fell just one point short of avoiding the drop having lost their last two matches.
Since then, another relegation followed for Arouca, but they have bounced back and go in search of top-flight football once again.
They take on a Rio Ave side who will be desperate to avoid the drop, having failed to break out of the bottom three on the final day of the regular season.
Os Rioavistas picked up a 2-1 away victory over basement side Nacional on the final day of the campaign, as Aderlan Santos equalised for the visitors following Dudu's early opener, before Carlos Mane netted the winner in the 94th minute.
However, that was not enough to move Miguel Cardoso's side out of the bottom three, as they finished one point short of Maritimo and Portimonense.
At the half-way mark of the season, Os Rioavistas did not look at all threatened by relegation, but an 11-game winless run, spanning from March until the victory on the final day, meant that they dropped into the battle for survival.
In that time, the Estadio dos Arcos side picked up just six points while scoring only five goals, playing a major factor in their final tally of 25 goals for the season being the joint-fewest in the top flight.
As a result, after five consecutive top-seven finishes in the Primeira Liga, Cardoso's men will have to battle over two legs to maintain their top-flight status.
Goals have been spread out across the Arouca squad this season, with centre-back Joao Basso and winger Andre Silva netting six this season, while fellow attackers Heliardo, Adilio Santos and Arsenio each have five goals.
Arsenio has also been somewhat of a creative hub for his side, registering four assists alongside five goals in his 21 league appearances.
Rio Ave could remain without experienced full-back Fabio Coentrao, who was absent from the squad for the final game of the season.
Their problems have mainly come in attack, with frontman Gelson Dala only netting three goals in 31 league appearances this season.
Winger Carlos Mane took his tally to six league goals for the season with the late winner last time out, and the former Sporting Lisbon man is the only player to pass five top-flight goals.
Arouca possible starting lineup:
Braga; Thales, Basso, Quaresma, Velazquez; Moreira, L Silva, Pite; A Silva, Arsenio, Santos
Rio Ave possible starting lineup:
Kieszek; Pinto, Santos, Borevkovic, Amaral; Guga, Augusto, Pele; Mane, Dala, Meshino
We say: Arouca 1-1 Rio Ave
The first leg of playoff encounters can often be cagey, and we see that happening on Wednesday as the sides jostle to gain the upper hand while staying conservative at the back.
The unique nature of a relegation playoff game means that the second-tier outfit come into this match with all of the momentum, having won their last nine games to reach this point, but we see Rio Ave avoiding defeat thanks to their Primeira Liga quality, especially at the back.