Ayoví started at lower division club Paladín "S". In 2006, his cousin Walter Ayoví recommended him to try out at Emelec. He did and was impressive enough to be signed on a 4-year deal when he was 18 years.
Despite his height and size he started playing as an open forward, or a winger and not as a center forward, because he is very skilled with the ball and very fast and he did not like to have to go down the middle but preferred to run to the sides where there was more space to move.
On 2009 he was loaned to first division club Manta to gain more minutes and experience. He did well playing in 32 matches of the Ecuadorian league and scoring 7 goals, despite this Emelec management were going to loan him again for the next season, but newly signed manager Jorge Sampaoli saw videos of Ayoví and requested him to stay in the 2010 squad, as a first substitution for the Argentinian striker Hernan Peirone.
As the 2010 season started it was becoming clear that Ayoví would have plenty more chances than expected and soon he became Sampaoli's first choice for the attack leaving Peirone in the bench. Ayoví did not disappoint and quickly started scoring important goals for his team, and was absolutely key to Emelec winning the first stage of the 2010 Ecuadorian tournament and reaching the final to be played in December 2010.
After the 2010 Ecuadorian season ended Jaime agree to join Mexican team Toluca on a three-year deal. He scored his first goal in his second appearance against Chiapas. On February 13 he scored his second in an emphatic 5–0 away win against Querétaro. He scored in a 3–2 home loss against Necaxa. On 13 February Ayovi scored an impressive header against Santos Laguna, in just under a minute of game time. Toluca won 3–1 at home turf. His final goal with Toluca came on 3 April and impressive solo effort, to draw the game against Monterrey 1–1.
After only half a season, Ayovi impressed the Pachuca manager, which sought to sign him for the team, Pachuca. His first goal for Pachuca was on 31 June, in a 2–2 away draw against Puebla FC. He would only score 3 more goals for the rest of the Apertura season against Cruz Azul, Estudiantes Tecos and Atlante FC. The 2012 Clausura would prove to be the same, scoring only 4 goals against Puebla, Cruz Azul, Querétaro and Chivas de Guadalajara. Due to his form with Pachuca, he was loaned to Saudi Arabian Premier League club Al Nassr.
Jaime Ayovi was loaned to Al Nassr FC for undisclosed fee which may lead up to the end of the Saudi Premier League season. On 29 September, Ayovi scored his first goal with Al Nassr, winning 3–1 against Al Wahda. He would go on to score 7 more goals for Al Nassr, including 2 doubles against Al Faisaly and Al Taawon, winning 2–1 and 3–2. His Saudi Premier League season was cut short when he was injured and was side-lined for 8 months. He finished his season with Al Nassr with 8 goals in 15 matches.
Northern Mexican football club Xolos de Tijuana signed Jaime Ayoví, with the agreement that he would be loaned to Ecuadorian giants LDU Quito for one full season, to fully recover his lost form due to injury.
Jaime Ayovi was given the number 11 jersey for his year-long stay at LDU Quito. On 17 August Ayovi scored his first goals, in a 2–2 home draw against Independiente del Valle. On 22 September Jaime scored his third in a 1–1 home draw against Macara. On October 3 he scored again in a 1–1 home draw versus Deportivo Quito. On 27 October Jaime scored his fifth goal with LDU Quito, in a 2–1 home win over LDU Loja. On November 10 Ayovi scored another double, this time in a 3–1 home win over Deportivo Quevedo.
On 7 March 2014, Ayoví scored his first goal for Tijuana against Guadalajara in a 2-0 Home Win. On 17 July 2014 it was confirmed that Ayoví would no longer fit the plans of the club.
On 14 August 2014, it was confirmed that Ayoví would play for Godoy Cruz on loan for 6 months.
On 20 February 2017, it was confirmed that Ayoví would play for Chinese League One side Beijing Renhe.
Ayoví was called by Ecuador's new manager, the Colombian Reinaldo Rueda, to defend the Ecuadorian national team for the first time for a match against Mexico in Guadalajara on 4 September 2010, he played well and he even managed to score Ecuador's second goal for an overall 2–1 victory.As of April 30, 2016
As of June 12, 2016
EmelecSerie A Runner-up (2): 2006, 2010
Emelec2010 Ecuadorian Serie A: Best Player
2010 Ecuadorian Serie A: Top goalscorer