Hohmann-Dennhardt comes on board as integrity officer.
The anti-corruption post was created last September after the company pleaded guilty to US bribery charges.
In April 2010 the company agreed to pay $185 million to settle US charges following a Foreign Corrupt Practices Act (FCPA) investigation into Daimler's worldwide sales practices.
Daimler admitted to making hundreds of improper payments worth tens of millions of dollars to foreign government officials in at least 22 countries between 1998 and 2008.
The appointment of the 60-year-old former regional minister comes amid debate on the possible introduction of quotas on the number of women employed by German firms.
Germany's family minister has warned companies that they have until 2013 to bring more women to their boards.
According to a recent study in the Die Welt daily newspaper, there are currently only a handful of women serving as board directors in the 30 companies listed on the DAX bourse, compared to 182 men.
There is no female chief executive officer among the top 100 German companies.