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 Espírito Santo 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.

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