The world number 16 from Germany has enjoyed a fruitful 2014, triumphing in Charleston and Bad Gastein on the WTA International Tour.
And the 27-year-old will be expected to mount a strong challenge for another title at the CK Sportcentre in Kockelscheuer as she attempts to build some momentum for the Tournament of Champions in Sofia, which commences at the end of the month.
Eugenie Bouchard and Ana Ivanovic were due to be the star attractions in Luxembourg, but both players pulled out due to injury.
Canadian rising star Bouchard withdrew from the Generali Ladies Linz this week due to leg injury and is taking no risks, having already qualified for the season-ending WTA Finals in Singapore.
World number eight Ivanovic also cut short her tournament in Linz, having been troubled by a hip problem and the Serb has also secured her place in the lucrative Singapore showpiece.
Their absence opens the door for the likes of Petkovic, who will be the top-ranked player in the draw and has played in this event on five previous occasions.
Her best performance in the Luxembourg Open came back in 2012, when she was beaten by Venus Williams in the semi-finals.
Last year's winner Caroline Wozniacki will not return to defend her title, but there will be a former champion on show in the form of Roberta Vinci - who took the title in 2010.
The Italian has failed to win a singles title this year, but can take heart from reaching the quarter-finals of the recent China Open - when she was beaten by Petra Kvitova.
World number 21 Alize Cornet will also be fancied to make an impact next week, as she targets her second title of the year.
Popular German Sabine Lisicki was a winner in Hong Kong last month and will be targeting a repeat performance in Kockelscheuer.