In May, less than a month after taking the job, Orcel reshaped top management, overhauling a structure designed by his predecessor Jean Pierre Mustier.
"Today's announcement is a further step in delivering on our objective to simplify and reduce the complexity that has shaped this business for too long," Orcel said in a statement.
Orcel arrived in mid-April after UniCredit's board fell out with his predecessor over strategy.
The bank is struggling with profitability after Mustier, a French investment banker, focused on repairing its balance sheet and shoring up capital reserves while failing to land a mooted cross-border merger.
Orcel, who is due to present a new business plan this year, has not ruled out possible mergers and acquisitions to help boost profit but is looking first to shake out bureaucracy.
"My focus for UniCredit at the moment is on the internal ... Not on the external, that is ... merely an accelerator," he said in a letter to employees seen by Reuters on Thursday.
UniCredit has been linked with a possible takeover of Italy's state-owned Monte dei Paschi di Siena, which Rome is looking to offload.
The latest move redesigns front-line management for each of the bank's business areas and regions to "reduce layering and complexities", UniCredit said in a statement.
In Italy, Barbara Tamburini will head the so-called Individuals operation, which includes the Mass Market, Affluent and Private Clients businesses, while Andrea Casini takes charge of the Enterprises operation.
Alfredo De Falco will lead Corporate Investment Banking (CIB) for Italy.
In Germany, Markus Beumer and Jan Kupfer will head the Enterprises and CIB units, respectively, while the new head of the Individuals unit will be announced in the near future, UniCredit said.
In Eastern and Central Europe, Pierre Yves Guegan will manage the retail business while Fabio Fornaroli will lead CIB.
The new structure also increases the diversity of the management team, mirroring the larger female presence on the group's executive committee, now up to 40% from the previous 15%.
(Reporting by Maria Pia QuagliaWriting by Stephen Jewkes, Editing by David Goodman and Paul Simao)
By Maria Pia Quaglia