A paradigm shift is taking place in the manufacturing sector where 3D printing is replacing the conventional manufacturing techniques for fabricating critical components owing to the numerous advantages offered by the 3D printing process. However, the multifold of associated process variables makes it imperative to characterize the 3D-printed components before their application in different fields. High strength-to-weight ratio and economical fabrication are the primary requirements while manufacturing these 3D-printed components, and therefore, metals are being replaced with 3D-printed high strength polymers and their composites. Fused deposition modeling (FDM) is the most widely accepted fabrication process for 3D printing these high-performance thermoplastics. Among the variety of thermoplastics, the 3D-printed polyether ether ketone (PEEK) has shown promising mechanical characteristics. However, there is still a need to analyze fracture behavior and crack growth in 3D-printed PEEK components under different stimuli. This current study deals with the implementation of a novel fracture behavior assessment technique called essential work of fracture (EWF) for characterizing the reliability and structural integrity of 3D-printed PEEK specimens under Mode-I loading conditions having 0° (material deposition path is parallel to the loading direction) and 90° (material deposition path is perpendicular to the loading direction) raster orientations. This article provides a fundamental guidance to design and materials engineers regarding the selection of the optimum raster orientation for 3D printing PEEK components with high fracture toughness.