Montero began formal piano lessons at age four with Lyl Tiempo, an Argentinian piano teacher who resided in Caracas, and gave her first public performance at the age of five. Aged eight, she made her concerto debut at the National Theater in Caracas performing the complete Haydn D Major Piano Concerto with the Orquesta Nacional Juvenil de Venezuela (National Youth Orchestra of Venezuela), conducted by José Antonio Abreu. This was the original youth orchestra created by Abreu in 1976, which would much later evolve into the orchestra presently known as the Simón Bolívar Youth Orchestra, an integral part of El Sistema, now known worldwide. At the age of nine, she was awarded a scholarship from the Venezuelan government to study in the US. From 1990 until 1993, she studied at the Royal Academy of Music in London with Hamish Milne.

Montero’s Bach and Beyond was given the “Choc de la musique de l’année” award in 2006 from the French magazine Le Monde de la musique. She also received the Keyboard Instrumentalist of the Year award at the ECHO Preis Award in Munich. In 2007, ECHO Preis awarded her the Klassik-ohne-Grenzen Award for her Bach and Beyond CD. In 2009, her album Baroque was nominated for a Grammy Award in two categories (Best Crossover Category and Best Producer Category). A more recent album (2015) – featuring her own composition for piano and orchestra “Ex Patria”, Rachmaninov’s Piano Concerto No.2, and 3 freestyle improvisations – won the Grammy for Best Classical Album at the 2015 Latin Grammy Awards. She has also been profiled on CBS’s 60 Minutes in a segment entitled “The Gift”.

Montero’s first CD release consisted of one disc of music by Rachmaninov, Chopin, and Liszt, and a second of improvisations. Her CD Bach and Beyond contains improvisations on Bach themes, and topped the charts for several months. In February 2008, her follow-up recording of improvisations, Baroque, received 5-star reviews from BBC Music Magazine and Classic FM.

Montero performed John Williams’ “Air and Simple Gifts” with Itzhak Perlman, Yo-Yo Ma, and Anthony McGill at the inauguration of U.S. president Barack Obama on January 20, 2009, although the music played was a recording made two days beforehand because of concerns over the cold weather damaging the instruments.

Montero has a long-established duo partnership with the French cellist Gautier Capuçon and they appeared at the 2009 Salzburg Festival and toured Germany in 2009 including engagements in Munich, Bonn, Hamburg, Dortmund and Heidelberg in April 2009 as well as the Théâtre du Châtelet, Paris, in May 2009. Future duo engagements in 2010 include the Vienna Konzerthaus, Braunschweig Festival, Beethoven Bonn Festival and Opéra de Lille.