As a Primeira Liga team, Rio Ave entered the 2013–14 Taça da Liga in the third round. The third round consisted of three group stage matches with the group winner progressing to the semi-finals. Rio Ave were drawn in group A, alongside Primeira Liga sides Paços de Ferreira, Vitória de Setúbal and Segunda Liga's Sporting da Covilhã. The Vilacondenses opening match was a home tie against fellow first division side Paços de Ferreira. Rio Ave defeated their opponents comfortably with goals in either half from Egyptian striker Ahmed Hassan and winger Ukra. Rio Ave's second group stage match saw the visit of Vitória de Setúbal to the Estádio dos Arcos. After trailing to a first half goal from Setúbal's Nélson Pedroso, Rio Ave's manager Nuno brought on three attacking minded players in the second half in order to salvage a point for the home side. Nuno's substitutions paid off, as six minutes from the end Joeano's free kick curled into the top corner and beat Vitória's Paweł Kieszek to postpone the decision of who would progress to the semi-finals for the last group stage match. For their final group stage match, Rio Ave played away to Sporting da Covilhã. In a must win match, Rio Ave defeated the Segunda Liga side 3–1 thanks to goals from Bruno Braga, Pedro Santos and Ukra to qualify for a second consecutive League Cup semi-final.
In the semi-finals, Rio Ave played host to group C winners Braga. In an evenly contested match, Rio Ave took the lead on 40 minutes through Ahmed Hassan, who converted from the penalty spot. The penalty came about after a long ball found an on rushing Bruno Braga who was fouled by Braga's Aderlan Santos. As Aderlan Santos was the last man of Braga's defense, match official Olegário Benquerença had no other option but to send off the Brazilian and reduce Braga to ten men. Replays showed that Santos did not make any contact with Braga, and that the foul occurred outside the penalty area. On the verge of half time, Braga equalized through Custódio, after Raul Rusescu's free kick was saved by Rio Ave's Ederson and Custódio was quickest to react to level the encounter at 1–1. Rio Ave would regain the lead on 69 minutes. A right wing cross from Ukra saw Braga fail to clear the ball on two occasions, which found Bruno Braga on the edge of the box and saw the midfielder strike a volley into Eduardo's right hand top corner to make it 2–1 to the home side. Despite Braga's late pressure, Rio Ave would hold on to reach the final of the Taça da Liga for the first time in their history.