In 1959, Chambers was out of school and looking for a purpose in life, so he ended up joining the United States Navy as an aviation electrician. After four years in the Service and acquiring the rank of Petty Officer Second Class - E-5, he returned home and started working at a South End bar that was owned by his mother. He worked for two months before being fired by his mother due to a scheduling mix-up.

When asked what car in his collection was his favorite, Chambers stated the 1972 Ferrari Daytona Spider that he owned in the early 1980s was his personal favorite.

In 1983, Chambers sold the A-Copy Business to Alco Standard Corporation for a reported $80 million and he continued to work with the company for another two years.

Chambers started his Automotive Business after purchasing a Cadillac dealership in New London, Connecticut, in 1985. His decision to purchase the Business was based on his own poor buying experience at the dealership. As Chambers improved the operations of this first car dealership, he started the Herb Chambers Companies.

In 2007, The Boston Globe carried an article and photo gallery highlighting Chambers' car collection. His collection of rare automobiles includes the McLaren F1, Mercedes-Benz SLR McLaren, Ferrari Daytona Spyder, Ferrari Daytona Coupe, 2006 Ford GT, 2008 Bugatti Veyron, Porsche 959 Supercar, 2006 Porsche Carrera GT, Cadillac Eldorado Biarritz Convertible, Ford Model B (1932) and a 1955 Mercedes-Benz 300SL that was raced in the 1983 Cannonball Run.

In 2016, Chambers helped to lead the effort to bring the Boston Police Department's mounted police unit back after it was disbanded in 2009 due to budget cuts. He was willing to donate $100,000 of the $1.5 million needed with the remaining funds would hopefully come from corporate support and city funding.

In August 2017, Chambers sold his 1995 McLaren F1 for $15.62 million at a Bonhams car auction held in Carmel, California.

After the Navy, Chambers began working as a copy machine repairman in Cambridge, Massachusetts for $75 a week, plus commission on any Service contracts he could sell. By the time he was 22, he had started his own copier distribution company called A-Copy America, with money borrowed from his parents, in Hartford, Connecticut. The copier Business was changing from a leasing model to a sales model due to the new low-cost copier Models from companies like Minolta, Canon, and Sharp and Chambers started selling copiers along with copy supplies. His Business soon became the world’s largest Minolta and Canon dealers with 1,400 employees in 36 offices.