Composites with different arrangements of continuous carbon fibers, with the poly(ethylene terephthalate)-spunbond nonwoven fabrics as substrates, were fabricated for optimization of electromagnetic interference shielding performance. Effects of these structural parameters, including array spacing, the number of layers, and overlap angle, were investigated within the frequency band of 30 MHz–1.5 GHz, which includes the major electromagnetic wave frequency from daily electronic device or apparatus. Within 30 MHz–750 MHz, shielding effectiveness was fortified with the decrease of array spacing and the increase of the number of layers owning to the increase of the continuous carbon fiber content. Whereas, within the frequency band of 750 MHz–1.5 GHz, the number of layers presented little effect on the shielding performance reasoning that the impact of continuous carbon fiber orientation was more significant than that of continuous carbon fiber content. While the array spacing was 8 mm and the maximum value of shielding effectiveness for the two-layer composites was 46.8 decibel at frequency of 1000 MHz. For multilayer composites, shielding performance was improved by synergistic effects of overlap angle and array spacing. Hence, composite with three layers, array spacing of 12 mm and overlap angle of 0°–0°–45° achieved the highest electromagnetic interference shielding properties of 60.49 decibel, corresponding frequency of 1.0 GHz. The results of this work demonstrated a potentially efficient and economical way to fabricate the electromagnetic interference shielding composites with less content of continuous carbon fiber and to simultaneously achieve superb shielding performance. This work will be significant for further study in the electromagnetic interference shielding composite industry in the near future.