Three-dimensional　(3D)　printing　of　continuous　fiber-reinforced　composites　has　been　developed　in　recent　decades　as　an　alternative　means　to　handle　complex　structures　with　excellent　design　flexibility　and　without　mold　forming.　Although　3D　printing　has　been　increasingly　used　in　the　manufacturing　industry,　there　is　still　room　for　the　development　of　theories　about　how　the　process　parameters　affect　microstructural　properties　to　meet　the　mechanical　requirements　of　the　printed　parts.　In　this　paper,　we　investigated　continuous　carbon　fiber-reinforced　polyphenylene　sulfide　(CCF/PPS)　as　feedstock　for　fused　deposition　modeling　(FDM)　simulated　by　thermocompression.　This　study　revealed　that　the　samples　manufactured　using　a　layer-by-layer　process　have　a　high　tensile　strength　up　to　2041.29　MPa,　which　is　improved　by　68.8%　compared　with　those　prepared　by　the　once-stacked　method.　Moreover,　the　mechanical–microstructure　characterization　relationships　indicated　that　the　compactness　of　the　laminates　is　higher　when　the　stacked　CCF/PPS　are　separated,　which　can　be　explained　based　on　both　the　void　formation　and　the　nanoindentation　results.　These　reinforcements　confirm　the　potential　of　remodeling　the　layer-up　methods　for　the　development　of　high-performance　carbon　fiber-reinforced　thermoplastics.　This　study　is　of　great　significance　to　the　improvement　of　the　FDM　process　and　opens　broad　prospects　for　the　aerospace　industry　and　continuous　fiber-reinforced　polymer　matrix　materials.　©　2022　by　the　authors.　Licensee　MDPI,　Basel,　Switzerland.