A quasi-experimental study with 256 German sixth-grade students examined the effects of exploring syntactic structures on literacy-related achievements. The core feature of the instruction was that students had the opportunity to deal with syntactic structures directly, not mediated by analytic operations. Instruction covered six lessons targeting two types of syntactic contrasts (syntactic category contrasts, noun case contrasts). The results indicate that students profited from the instruction in their ability to use a marker of syntactic structure in written German, the capitalization of nouns. As to the ability to use the same marker to interpret text read, students of different achievement levels seem to have been differently affected. No effects were found for reading comprehension in general and spelling at the word level. The findings suggest that students’ recognition of syntactic categories was enhanced even in contexts other than those they were familiarized with in the instruction. However, it was not enhanced when they worked on a task that was completely new to them.