La Tri suffered a 2-0 defeat to hosts Chile on the opening night of the competition, while El Verde picked up a point against invitees Mexico the following day.
Subsequently, Gustavo Quinteros' men are rooted to the bottom of the Group A table.
They now will kick off the second round of fixtures when they face Mauricio Soria's side at the Estadio Elías Figueroa Brander.
And Valencia knows that La Tri cannot afford to leave without a result, which he feels they need more than Bolivia, and he expects his side to play in an attacking fashion."Our coach likes to have a team that goes on the attack and looks for the opponent and I think that it will be very important to have this attitude in the match with Bolivia," he said.
"We are confident that against Bolivia we can do better things. The two teams are in need of a win, but us more because we still don't have any points."
The results of the previous clashes between the two sides at the Copa América are evenly split, with one victory each and five draws from their seven meetings, but in all competitions Ecuador have been far superior - not losing to El Verde in 11 fixtures.
In order to continue that run in Valparaíso, though, Walter Ayoví believes that la Tri need to work on the errors from their last outing."The team knows that we made mistakes against Chile and we hope that we can work on rectifying that. The important thing is that on Monday we can have a good game," added the captain.
Their cause may be aided in the fact that Bolivia have two key players struggling following their Group A debut.
Marcelo Martins (foot) and Jhasmani Campos (thigh) picked up knocks in the meeting with Mexico, though the seriousness of their issues is yet to be confirmed.