Rodriguez took over the presidency on an interim basis earlier in January after the US military captured President Nicolas Maduro and flew him to the United States to stand trial for drug charges.
Trump, in a post on social media on Wednesday, said the two discussed oil, minerals, trade and security, as the US worked to "help Venezuela stabilise and recover".
The call marks a dramatic diplomatic shift between the two countries after months of escalating tensions, including US military strikes on alleged drug trafficking vessels and sanctions targeting Venezuela's oil sector, as the Trump administration eyes the country's vast but underproducing oil reserves.
Rodriguez, Maduro's former vice president, called the call long, productive and courteous and said the two discussed a bilateral agenda for the benefit of both countries.
In recent days, Rodriguez has slammed the Trump administration for "kidnapping" Maduro and called for his return.
Trump, in his own remarks about the call, said Rodriguez was a "terrific person" and that US Secretary of State Marco Rubio had also been in touch with her.
Meanwhile, Venezuela's government says 116 prisoners have so far been released, though rights groups report a lower figure as family members of the detained await liberations, with some sleeping outside prisons.
Unidad Venezuela, a group of opposition parties, said just 65 people had been freed so far, urging the Venezuelan government in a post on X to "speed up the release process so that the suffering of political prisoners and their families can finally come to an end".
Legal advocacy group Foro Penal had a count of just 49.
The government figure, published by the Penitentiary Services Ministry, followed three days of reports from rights organisations about delays in releases.
The ministry said those being freed had been involved in "acts associated with disrupting the constitutional order and undermining the stability of the nation".
Supporters and family members have spent the weekend gathering at detention centres throughout the capital Caracas, where they also held candlelit vigils and some stayed overnight on mattresses outside, hoping to see their loved ones set free.
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