Martha Erika Alonso, the new governor of the central state of Puebla, was killed just 10 days after taking office. Her husband, Senator Rafael Moreno, who was a former governor for the same state as his wife, was also killed. Ms Alonso was the first female to be elected as governor of Puebla.
Mr Moreno also served as governor between 2011 and 2017.
The crash occurred shortly after takeoff, not far from the state capital Puebla.
It is unclear if the pilot died.
The cause of the crash is currently unknown.
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The president of the centre-right National Action Party (PAN), of which the pair were members of, paid his respects on Twitter.
Marko Cortes wrote: “May they rest in peace; The PAN is in mourning.”
Mexico’s newly elected President, Andrés Manuel López Obrador, also expressed his “deepest condolences” social media.
He said: “Personally, my deepest condolences to the relatives of Senator Rafael Moreno Valle and his wife, the governor of Puebla, Martha Érika Alonso.
“As President, I am committed to investigating the causes to find out the truth about what happened and act accordingly.”
The crash involving Ms Alonso and Mr Moreno is not the first time Mexican politicians have died in aircraft accidents.
Two federal interior ministers also died in crashes in 2008 and 2011.
They were both members of the same party at Ms Alonso and Mr Moreno.