Tillerson's visit was the first leg of a seven-day trip to Mexico, Peru, Argentina, Jamaica and Colombia.
But, when he sits down on Friday with Peña Nieto and his Canadian counterpart Chrystia Freeland the trade deal will be in the foreground of their agenda, and he has adopted an optimistic approach, whatever Trump's rhetoric.
Tillerson also talked about the USA helping law enforcement in Mexico - providing inspection equipment and training - to help put an end to smuggling of drugs and people.
Issuing an ambiguous threat to Venezuela, US Secretary of State Rex Tillerson said the army has often been an "agent of change" in the Latin American country and beyond in cases when leadership "can no longer serve the people".
Speaking at the University of Texas at Austin ahead of a five-country swing through Latin America and the Caribbean, Tillerson said he did not know whether a military ouster of Maduro would happen, but he hoped change would happen peacefully.
The trip will be an effort to reassure nations that the US remains interested in a region that under President Donald Trump is mentioned mostly as a source of illegal immigrants and crime. "Our nations still reflect the New World optimism of limitless discovery", he told staff and students.
During the South American part of the trip, Tillerson is expected to rally the region's governments in pressing for democratic reforms in Venezuela.
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"And importantly, we share democratic values, values that are the core of what we believe, regardless of the color of our passport". The latest national election held in Venezuela - the one that led to the inauguration of the National Constituent Assembly in August - was not recognized by Washington, which slapped the country with several rounds of sanctions targeting the financial and energy sectors of the oil-rich country. "In their pursuit of money and power, TCOs leave death and destruction in their wake".
He said Latin America does not need new imperial powers that seek only to benefit their own people.
Tillerson also criticized Russian Federation for selling weapons to authoritarian governments in Latin America.
As popular outrage mounted, President Maduro and his government said the protests had been inspired from overseas, suggesting that outside pressure played a role in making the country's economic hardship even worse.
The United States will use "all its political, diplomatic and economic tools to address the situation in Venezuela", a senior State Department official said at a briefing this week on the trip.
"The corrupt and hostile regime of Nicolas Maduro in Venezuela clings to a false dream and antiquated vision for the region that has already failed its citizens", Tillerson said Thursday at the University of Texas at Austin during a stop en route to Mexico. The continent's major powers reject the regime but are cautious about piling on the more economic misery with Venezuela on the brink of chaos.
After his speech, Tillerson will head to Mexico City, Mexico.