On 3 August 2013, President Nicolás Maduro appointed her as the Minister of Popular Power for Communication and Information of Venezuela, a position in which she was reaffirmed in 2014 and maintained until 13 October 2014.

On 26 December 2014, President Nicolás Maduro appointed Rodríguez as the Minister of Popular Power for Foreign Relations, also known as Chancellor, succeeding Rafael Ramírez Carreño.

During this summit, Rodríguez was involved in a dispute with the President of Argentina, Mauricio Macri, who called for the prompt release of political prisoners in Venezuela.

[18][19] Rodríguez alleged Macri had released prisoners who were responsible for repression during the last military dictatorship in Argentina and had vetoed laws aimed at addressing unfair treatment, torture, and forced disappearances.

On 24 June 2016, during the commemoration of the 195th anniversary of the Battle of Carabobo, President Nicolás Maduro awarded Rodríguez the Military Order of National Defense, Commander Degree, First Class.

At the XXV Ibero-American Summit of Heads of State and Government, which took place in Cartagena de Indias, Colombia, Rodríguez addressed the President of Peru, Pedro Pablo Kuczynski.

The trio expressed reservations regarding Venezuela's compliance with the prerequisites for full membership within the bloc, emphasizing the need for adherence to Mercosur's stipulations, particularly in the areas of trade, politics, democracy, and human rights.

[23] On 14 December 2016, Rodríguez attempted to attend a Mercosur summit in Buenos Aires, Argentina, accompanied by the then Foreign Minister of Bolivia, David Choquehuanca.

[27] Before she left her position, on 22 June, President Nicolás Maduro honored her with the Saber Order of the Liberator Simón Bolívar of the Battle of Carabobo.

[30] On 7 February, Rodríguez resigned from the United Socialist Party of Venezuela (PSUV) and joined the ranks of the MSV, adhering to statutes prohibiting dual membership in political organizations within the country.

[34] Since 10 September 2020, Rodríguez has served as the Minister of Popular Power for Economy and Finance of Venezuela, having been appointed to this position by President Nicolás Maduro.

In July 2021, Rodríguez participated in the Annual Assembly of Fedecámaras, marking the first instance in two decades that a high-ranking official from the national executive attended this event, which convenes leaders from the country's main corporations.

Rodríguez highlighted the significance of private sector engagement in unlocking Venezuela's productive capacity but urged the business community in attendance to refrain from political involvement.

[35] The stance and demeanor of the businessmen during the event drew significant critique from opposition politicians and leaders of civil society, and according to El País, it was also met with disapproval by numerous social media users, who perceived it as a surrender amid a state of profound necessity.

[45][46][47] The United States sanctioned Rodríguez on 25 September 2018 for "corruption and humanitarian issues" by including her in OFAC's Specially Designated Nationals and Blocked Persons List.

Accompanying Rodríguez on the flight were Kenny Antonio Díaz, Alejandra Carolina Bastidas, Yussef Abou Nassif Smaili (her partner), Jorge Andrés Giménez (the current president of the Venezuelan Football Federation), and Minister Félix Plasencia.

[52] This transaction was purportedly conducted through the Spanish Ministry of Transport, with the involvement of then-Transport Minister José Luis Ábalos, who is currently under investigation in the "Caso Koldo."

[52] The Guardia Civil’s Central Operative Unit (UCO) uncovered communications on Spanish businessman Víctor de Aldama's mobile phone that directly linked him to Rodríguez, indicating discussions about the purchase of Venezuelan gold.

Additionally, messages exchanged between Rodríguez and Aldama suggested a personal and potentially corrupt relationship, as evidenced by friendly remarks following the failed transaction deadline.

[52] The scandal also involved a strategic omission of the gold transaction details in the official invitation sent by Ábalos to Rodríguez, which instead focused on humanitarian aid and support for Spanish businesses in Venezuela.

In response, the Spanish opposition’s Partido Popular accused Prime Minister Sánchez of deceit regarding the true purpose of Rodríguez's visit and declared intentions to launch a comprehensive political, judicial, and international campaign to uncover the truth behind Delcygate.