Sterling's star on the Hollywood Walk of Fame is located at 1709 Vine Street.

Sterling is perhaps most well known for starring with Jeffreys as the spirited George Kerby, to Jefferys' Marion Kerby in the television program Topper, based on the original 1937 film of the same name. It aired on the CBS network from 1953 to 1955. Leo G. Carroll starred in the title role. Wife Marion Kerby was referred to as "the ghostess with the mostest", while Sterling's character was known as "that most sporty spirit".

He was in Only Angels Have Wings (1939), Missing Daughters (1939), and a short with Buster Keaton, Pest from the West (1939). Sterling was in Good Girls Go to Paris (1939), The Man They Could Not Hang (1939), Golden Boy (1939), The Gates of Alcatraz (1939), A Woman is the Judge (1939), The Story of Charles Goodyear (1939), Scandal Sheet (1939), Mr Smith Goes to Washington (1939), Beware Spooks! (1939), Blondie Brings Up Baby (1939), The Amazing Mr Williams (1939), Glove Slingers (1939), The Awful Goof (1939) (a short), and Crime's End (1939).

In November 1940 , Sterling went to Metro-Goldwyn-Mayer. He appeared in The Penalty (1941) and had the lead in I'll Wait for You (1941), The Getaway (1941), and Ringside Maisie (1941) with Ann Sothern, who he would later marry.

He had a good support role in Two-Faced Woman (1941) with Greta Garbo and Johnny Eager (1941) with Robert Taylor. Sterling could also be see in Dr. Kildare's Victory (1942) and This Time for Keeps (1942). He was billed third in Somewhere I'll Find You (1942), after Clark Gable and Lana Turner - one of MGM's biggest films of the year. But just as it seemed Sterling was about to breakthrough as a star he joined the services.

Sterling was married twice. His first marriage, in 1943, was to noted actress-singer Ann Sothern. They had a daughter, Patricia, who became an Actress. Sothern and Sterling divorced in 1949.

Sterling served in World War II as a United States Army Air Corps FLIGHT instructor. He got out of the army in October 1945 and MGM announced him for The Last Time I Saw Paris but the film would not be made for several years, without Sterling. He appeared in The Secret Heart (1946) at MGM.

At RKO he had the lead in Roughshod (1949). He made an independent Western, The Sundowners (1950) and did Bunco Squad (1951) at RKO.

Sterling met actress-singer Anne Jeffreys soon after his Broadway debut, and they wed in 1951 and remained married for 55 years until his death. They had three sons.

In 1955 he and Jeffreys appeared in a TV production of Dearest Enemy, adapted by Neil Simon. He continued to guest star on shows like The Loretta Young Show, Lux Video Theatre, Star Stage, The 20th Century-Fox Hour, The Ford Television Theatre, Cavalcade of America, and Telephone Time.

On December 18, 1957, Sterling and Jeffreys played a couple with an unusual courtship arrangement in "The Julie Gage Story" on the first season of NBC's Wagon Train.

In 1958, the couple co-starred in another comedy series, Love That Jill on ABC. Sterling and Jeffries portrayed heads of rival modeling agencies in New York City.

After some additional television work in the early 1960s, Sterling made only sporadic appearances in later shows such as the hospital drama The Bold Ones, the sitcoms Nanny and the Professor, Love, American Style, Diana and The Brian Keith Show, the TV movie Letters from Three Lovers (1973), and the miniseries Beggarman, Thief in 1979.

In the 1961–1962 television season, Sterling co-starred with George Chandler and Reta Shaw in CBS's Ichabod and Me, a sitcom set in New England. He portrayed 44-year-old Bob Major, a newspaper reporter from New York City, who purchased and ran the paper in a small town called Phippsboro.

In 1963, Sterling starred in The Twilight Zone episode "Printer's Devil" alongside Burgess Meredith. He was also in The Alfred Hitchcock Hour and Naked City, plus A Global Affair (1964) with Bob Hope.

In the 1970s Sterling ling was a vice President and the spokesman for a company that implemented the software for one of the first supermarket barcoding and computer inventory systems. He later launched Sterling & Sons, a Santa Monica company that manufactured custom golf clubs.

In the 1980s he guest starred on shows like Fantasy Island, Simon & Simon, Masquerade, Murder, She Wrote, and Hotel.

Sterling died Tuesday, May 30, 2006, aged 88, at his home in Brentwood, Los Angeles, California. According to the Associated Press, his son, Jeffrey, indicated that Sterling died of natural causes and also suffered from debilitating shingles for the last decade of his life.