Brenda Delgado faces a charge of capital murder and unlawful flight to avoid prosecution, following the death of dentist Dr Kendra Hatcher in September.
Miss Hatcher, 35, was shot in the head in the car park of an apartment block in Dallas, Texas, with police accusing Delgado of hiring accomplices to carry out the killing.
Police have arrested two other people in the case, the accused gunman Kristopher Love and the alleged getaway car driver Crystal Cortes.
Investigators say Delgado was jealous because Miss Hatcher was dating her ex-boyfriend Ricardo Paniagua and had recently been introduced to his parents.
Delgado, 33, had dated Mr Paniagua, a dermatologist, for two years.
Police had questioned her within days of the shooting but let her go because of a lack of evidence.
Delgado was arrested at a house in the city of Torreon, in northern Coahuila state, according to the Attorney General's Office.
She will be held in a Mexico City jail until an extradition hearing.
The Mexican-born naturalised US citizen is only the ninth woman to be put on the FBI's Most Wanted list since it was created in 1950.
Federal investigators had told a news conference on Wednesday that they were offering a $100,000 reward for her arrest.
Source: Skynews
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