Connelly and Alba are Revlon spokeswomen. The race is to take place May 2 in New York.
Christina Applegate, Miley Cyrus, her mother Tish Cyrus, Revlon spokeswoman Beau Garrett and Carrie Ann Inaba are set to join take part the Los Angeles version of the event May 9.
The Entertainment Industry Foundation's Revlon Run/Walk is one of the nation's largest single-day fundraisers to support women's cancer research, counseling and outreach programs in New York and Los Angeles, organizers said.
"Hundreds of thousands of women and men have come out year after year to support the cause and for loved ones who have been personally affected by cancer. Their devotion and commitment to finding a cure is what has made the EIF Revlon Run/Walk so successful," Ronald O. Perelman, chairman of Revlon, Inc., co-founder of the Run/Walk and co-founder of the Revlon/UCLA Women's Cancer Research Program, said in a statement. "Through significant advancement in education and research, so many women today are finding resources and treatments made available to them and with that aid they are beating the odds and surviving cancer."