The 25-year-old will leave Porto and join los Che in the summer on a five-year deal and revealed his delight at joining the club
The 25-year-old, who will join the club in July, has been highly sought-after, with a number of European clubs interested in the Argentine's services, including Manchester United, Manchester City and Monaco.
And the centre-back was thrilled to join a club with previous Argentine greats such as Mario Kempes, Roberto Ayala and Pablo Aimar.
“After playing for a club like Porto - a huge, prestigious club - it is an honour to join a club like Valencia for this next stage of my career," Otamendi told the official club website.
"Valencia are one of the most historic and attractive teams in Spain and in Europe, and I am very happy with this next step in my footballing life.
“I know that Argentine players have been an important part of Valencia CF’s history. To wear the same shirt as Mario Kempes, Roberto Ayala, Pablo Aimar and many more is a responsibility that I will take on with much joy and excitement.
The club's general sporting manager Francisco Rufete added: “We have a great squad and we are convinced that Nico Otamendi will help us to improve from next season onwards, because he is a world-class talent.
"He is a strategic incorporation for our project and we are fortunate that he has chosen Valencia out of the many clubs vying for his signature. The arrival of Otamendi is great news for all Valencianistas and for the future of our side.”