After shepherding Germany through Europe's lengthy financial turmoil, Merkel has emerged more popular than ever, proving a safe pair of hands as the crisis felled leaders in France, Greece, Italy and Spain.
Polls suggest that voters will re-elect the 59-year-old pastor's daughter, whose nickname "Mutti" ("Mummy") can seem at odds with her other often-used description as the world's most powerful woman.
But the burning question is whether she will be able to keep her preferred coalition partner or be forced into an alliance with her centre-left rivals.
"I think we have a good standard of living in Europe and for me, this must remain stable. So, to me, voting for the extremes, on the left or the right, isn't an answer," nun Elisabeth Bauer told AFP.
Maressa Kutscha, 26, admitted it had been a struggle to choose.
"I was extremely uncertain voting... Because not much differentiates the parties," she said.
Nearly 62 million voters were called to the polls. Initial television estimates are expected shortly after booths close at 6:00 pm local time (2130 IST).
Merkel boasts her current centre-right coalition has been Germany's most successful since reunification in 1990, enjoying a robust economy and a jobless rate of less than seven per cent.
But her stated aim for her conservative Christian Democratic Union (CDU) to stay in power with its junior partners, the pro-business Free Democratic Party (FDP), hinges on the smaller party's unpredictable fortunes.
"The continued governing by this coalition remains uncertain," said Gero Neugebauer, a political scientist from Berlin's Free University.
Under the watchful eye of Germany's European partners, a new eurosceptic party, the Alternative for Germany (AfD), could also prove a wild card, either by clawing enough support to send MPs into parliament or wooing away disgruntled centre-right voters.
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