Relative clause (RC) formation and center embedding (CE) are two primary syntactic operations fundamental for creating and understanding complex sentences. Ample evidence from previous cross-linguistic studies has revealed several similarities and differences between RC and CE. However, it is not easy to investigate the effect of pure syntactic constraints for RC and CE without the interference of semantic and pragmatic interactions. Here, we show how readers process CE and RC using a self-paced reading task in Korean. More interestingly, we adopted a novel self-paced pseudoword reading task to exploit syntactic operations of the RC and CE, eliminating the semantic and pragmatic interference in sentence comprehension. Our results showed that the main effects of RC and CE conform to previous studies. Furthermore, we found a facilitation effect of sentence comprehension when we combined an RC and CE in a complex sentence. Our study provides a valuable insight into how the purely syntactic processing of RC and CE assists comprehension of complex sentences.