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"When I Look at You" peaked at number 16 on the Billboard Hot 100 and charted within the top 30 on charts in Australia, Canada, and New Zealand. The song's accompanying music video was directed by Adam Shankman. It features Cyrus playing a grand piano throughout several settings, including a beach and forest. Two other versions of the video were released: one replacing several scenes with clips from The Last Song and another featuring Bisbal. The song was included on her first world tour, the Wonder World Tour (2009)
"When I Look at You" was written by Hillary Lindsey and John Shanks. It was used to promote the 2010 film The Last Song, in which Cyrus stars as Veronica "Ronnie" Miller, an angry, rebellious adolescent forced to spend a summer with her estranged father. The song was first included on Cyrus's 2009 extended play The Time of Our Lives and then on the film and its corresponding soundtrack. The song was initially to be included on Cyrus's 2010 album Can't Be Tamed; however, it was decided to include it on the The Time of Our Lives as well as The Last Song because it fit the film's concept well. According to Cyrus, when she sings "When I Look at You", she thinks of family and love. "It's kind of what this movie is all about", she said. A remix version titled "Te Miro a Ti", featuring Spanish singer David Bisbal was released later; in it, Cyrus sings her lines in English, while Bisbal's are mingled in both English and Spanish.
"When I Look at You" is a pop song with a length of four minutes and eight seconds. According to Katie Byrne of MTV News, the song is a power ballad. The song is set in 3 4 time and has a moderate tempo of 138 beats per minute. It is written in the key of G-flat major and Cyrus's vocals span two octaves, from G3 to E5. The song begins with piano in its intro and then transitions to Cyrus singing in a hushed tone. She begins to belt towards the second verse and an electric guitar solo follows the second chorus, showing the influence of country music on the song. It follows the chord progression E♭m–G♭–D♭–C♭–C♭. Jocelyn Vena, also of MTV News, interpreted the lyrics of "When I Look at You" to be about Cyrus' dream boy. According to Byrne, the last line — "You appear just like a dream to me" — is very fantasy-like.
Reception from contemporary critics for the song has been average to mixed, with Variety magazine's Lael Lowenstein calling it an "almost inevitable hit single", and Allmusic's Heather Phares noting that "When she lets her ... ballad-singing diva come to the fore, Cyrus really shines." Phares added, "She is just as accomplished on the EP's ballads". Bill Lamb of About.com disagreed and stated, "the two ballad songs, 'When I Look At You' and 'Obsessed,' feel like throwaways. Miley Cyrus did have a big hit with the highly inspirational 'The Climb,' but the ballads here flush out the distinctiveness in her voice and simply feel ordinary." Michael Hann of the English newspaper The Guardian referred to "When I Look at You" as one of the "inferior ballads" on The Time of Our Lives. The song won the 2010 Teen Choice Award for "Choice Music: Love Song"
In the United States, on the week ending January 23, 2010, "When I Look at You" debuted at number 88 on the Billboard Hot 100. On the week ending April 17, 2010, "When I Look at You" ascended to its peak at number 16, from its previous position at number 25, on the Billboard Hot 100. The song peaked at number 18 on Billboard 's Adult Contemporary Chart. The song first appeared on the Canadian Hot 100 at number 59 and peaked at number 24. As of June 2013, "When I Look At You" has sold 1,319,000 copies in the United States.
The song also made moderate success in Australia and New Zealand. The song entered the Australian Singles Chart at number 50 and, after three weeks of ascending the chart, reached its peak at number 19. In New Zealand, "When I Look at You" debuted and peaked at number 27. The song debuted at number 79 on the UK Singles Chart. On the week ending April 1, 2010, it debuted and peaked at number 45 on the Irish Singles Chart. In mainland Europe, "When I Look at You" peaked at number 23 on the Belgian Tip Singles Chart (Wallonia) and number 49 on the Swiss Singles Chart.