| Year | Pitcher (Team) | ERA |
| 1968 | Bob Gibson - St. Louis Cardinals | 1.12 |
| 1985 | Dwight Gooden - New York Mets | 1.53 |
| 1994 | Greg Maddux - Atlanta Braves | 1.56 |
| 1968 | Luis Tiant - Cleveland Indians | 1.60 |
| 1995 | Greg Maddux - Atlanta Braves | 1.63 |
| 1943 | Spud Chandler - New York Yankees | 1.64 |
| 1964 | Dean Chance - Los Angeles Angels | 1.65 |
| 1933 | Carl Hubbell - New York Giants | 1.66 |
| 1981 | Nolan Ryan - Houston Astros | 1.69 |
| 1966 | Sandy Koufax - Los Angeles Dodgers | 1.73 |
| 1964 | Sandy Koufax - Los Angeles Dodgers | 1.74 |
| 1978 | Ron Guidry - New York Yankees | 1.74 |
| 2000 | Pedro Martinez - Boston Red Sox | 1.74 |
| 1971 | Tom Seaver - New York Mets | 1.76 |
| 1942 | Mort Cooper - St. Louis Cardinals | 1.78 |
| 1944 | Hal Newhouser - Detroit Tigers | 1.81 |
| 1968 | Sam McDowell - Cleveland Indians | 1.81 |
| 1971 | Vida Blue - Oakland Athletics | 1.82 |
| 1967 | Phil Niekro - Atlanta Braves | 1.87 |
| 2005 | Roger Clemens - Houston Astros | 1.87 |
| 1963 | Sandy Koufax - Los Angeles Dodgers | 1.88 |
| 1964 | Joe Horlen - Chicago White Sox | 1.88 |
| 1996 | Kevin Brown - Florida Marlins | 1.89 |
| 1943 | Max Lanier - St. Louis Cardinals | 1.90 |
| 1997 | Pedro Martinez - Montreal Expos | 1.90 |
| 1920 | Pete Alexander - Chicago Cubs | 1.91 |
| 1971 | Wilbur Wood - Chicago White Sox | 1.91 |
| 1972 | Luis Tiant - Boston Red Sox | 1.91 |
| 1972 | Gaylord Perry - Cleveland Indians | 1.92 |
| 1923 | Dolf Luque - Cincinnati Reds | 1.93 |
| 1985 | John Tudor - St. Louis Cardinals | 1.93 |
| 1990 | Roger Clemens - Boston Red Sox | 1.93 |
| 1945 | Hal Newhouser - Detroit Tigers | 1.94 |
| 1968 | Dave McNally - Baltimore Orioles | 1.95 |
| 1968 | Denny McLain - Detroit Tigers | 1.96 |
| 1955 | Billy Pierce - Chicago White Sox | 1.97 |
| 1972 | Steve Carlton - Philadelphia Phillies | 1.97 |
| 1966 | Gary Peters - Chicago White Sox | 1.98 |
| 1968 | Tommy John - Chicago White Sox | 1.98 |
| 1968 | Bobby Bolin - San Francisco | 1.99 |
| 1972 | Gary Nolan - Cincinnati Reds | 1.99 |
