Goldstein, who worked closely with Bealefeld, said in an email that it had been a "privilege to serve Mayor Stephanie Rawlings-Blake and the citizens of Baltimore." Goldstein said "it was just time to move on to something new." Her last day will be June 15, she said.
"I have had the honor of working with a terrific team of dedicated people throughout my tenure," she said in an email. "I hope that during my time I have made a contribution to assisting victims and making our city safer. I am looking forward to having some time off."
A mayoral spokesman referred questions to Goldstein.
Former Mayor Sheila Dixon, who tapped Goldstein in 2006 to head the Mayor's Office on Criminal Justice, praised her as "very talented." Rawlings-Blake retained Goldstein in her Cabinet when she took office in 2010.
"She really put that [crime-fighting] plan in place," said Dixon. "She went after grant money and helped us get a lot of grants."
Goldstein's husband is Gregg L. Bernstein, the state's attorney for Baltimore. Goldstein took a leave of absence during her husband's 2010 campaign for the state's attorney's office. Before being tapped by Dixon, Goldstein held a similar position in Baltimore County government.
Bealefeld and Goldstein are the most recent in a series of high-level departures from the Rawlings-Blake administration.
Former Deputy Mayor Christopher Thomaskutty, who oversaw public safety and worked closely with Bealefeld and Goldstein, left City Hall last month to take a job at Mercy Medical Center.
Peter O'Malley, Gov. Martin O'Malley's brother, resigned from his position as Rawlings-Blake's chief of staff soon after Thomaskutty announced his departure. Peter O'Malley now works for the Venable law firm.
Rawlings-Blake appointed Thomasina Hiers as interim chief of staff after O'Malley left. Weeks later, Hiers said she was leaving for a job in state government, where she had worked previously.
Gregory A. Bayor, whom Rawlings-Blake had selected to lead the Recreation and Parks Department two years ago, left to take a job in Florida last month. Longtime city Finance Director Edward Gallagher retired this year. The head of the Baltimore Development Corp., M.J. "Jay" Brodie, plans to retire after the mayor chooses a new leader for the city's quasi-public economic development arm.
Other recent departures include Carla Nelson, head of the Office of Minority and Women-Owned Business Development; Human Resources Director Gladys Gaskins; and Shirley Williams, chief of the Minority and Women's Business Opportunity Office.
Rico Singleton, whom Rawlings-Blake chose to head the Mayor's Office of Information Technology, resigned in February after the release of a New York state audit that alleged numerous ethics violations under his watch there.
News of Goldstein's resignation broke as current and former City Hall employees were at a party to celebrate the departure of another colleague, Public Works spokeswoman Celeste Amato.
Baltimore Sun reporters Peter Hermann and Justin Fenton contributed to this article.