The striker was widely expected to join Real Madrid on a free transfer as he continued to run down the final few weeks of his previous contract with the French champions.
However, Mbappe stunned the footballing landscape by agreeing to a new three-year deal at the Parc des Princes, tying him to Les Parisiens until the end of the 2024-25 season.
La Liga labelled Mbappe's lucrative new deal - believed to be worth €40m (£34m) per year "scandalous" - while president Tebas described it as an "insult to football".
The Spanish division also announced its intention to formally complain to UEFA about Mbappe's new contract, claiming that PSG had "no respect" for the game.
"LaLiga wishes to state that this type of agreement attacks the economic stability of European football, putting at risk hundreds of thousands of jobs and the integrity of the sport, not only in European competitions, but also in domestic leagues," the statement read.
"LaLiga will file a complaint against PSG before UEFA, the French administrative and fiscal authorities and European Union authorities to continue to defend the economic ecosystem of European football and its sustainability.
"This behaviour demonstrates once more that state owned clubs do not respect and do not want to respect the rules of a sector as important as football. These rules are key to protect and sustain hundreds of thousands of jobs.
"This kind of behaviour led by Al-Khelaifi, president of PSG, and member of the UEFA Executive Committee and president of ECA, endangers European football on the same level as the European Super League."
Al-Khelaifi and Mbappe held their first press conference since the latter's contract signing on Monday afternoon, and the former believes that Tebas is concerned about the threat of Ligue 1 becoming a more attractive competition than La Liga.
"I think he (Tebas) is maybe scared of Ligue 1 becoming bigger than La Liga. That's a good thing for us. It is a positive for us as a club," Al-Khelaifi told reporters.
"La Liga isn't what it was three or four years ago. We have a lot of respect for all of the clubs in La Liga as well as for the championship, but we need to be respected as well. We have Mbappe, he stays with us and the rest, honestly I don't care."
The PSG president also confirmed that the club would be active in the summer transfer market following Mbappe's renewal, and the 23-year-old revealed that he had held talks with French president Emmanuel Macron, who helped persuade him to stay put.
Mbappe celebrated his new contract by bagging a hat-trick in Saturday's 5-0 thrashing of Metz, seeing him end the Ligue 1 season top of the goals and assists charts with 28 strikes and 17 assists.
The former Monaco starlet has now amassed a total of 171 goals and 87 assists in 217 games for Mauricio Pochettino's side since initially arriving on loan in the summer of 2017. body check tags ::