Previous research has shown effects of syntactic complexity on sentence processing. In linguistics, syntactic complexity (caused by different word orders) is traditionally explained by distinct linguistic operations. This study investigates whether different complex word orders indeed result in distinct patterns of neural activity, as would be expected when distinct linguistic operations are applied. Twenty-two older adults performed an auditory sentence processing paradigm in German with and without increased cognitive load. The results show that without increased cognitive load, complex sentences show distinct activation patterns compared with less complex, canonical sentences: complex object-initial sentences show increased activity in the left inferior frontal and temporal regions, whereas complex adjunct-initial sentences show increased activity in occipital and right superior frontal regions. Increased cognitive load seems to affect the processing of different sentence structures differently, increasing neural activity for canonical sentences, but leaving complex sentences relatively unaffected. We discuss these results in the context of the idea that linguistic operations required for processing sentence structures with higher levels of complexity involve distinct brain operations.