Delamination is a common failure mode observed in fiber reinforced polymeric composites subjected to thermo-mechanical loads. Reinforcements at the interlaminar regions or in the through-thickness direction have been previously shown to improve the damage resistance and durability of these composites. In particular additive manufacturing (AM), also called 3D printing, has been shown to increase the interlaminar shear strength when used for custom printing of polymer reinforcements over carbon fiber prepreg prior to the layup process of layered composites. In this paper, printing of interlaminar polymer reinforcements using fused deposition modeling (FDM) technique within AM is proposed for improving the interlaminar fracture toughness of carbon fiber laminates. The rationale behind this improvement in the interlaminar fracture toughness values due to printed polymer reinforcements (PPR) is investigated by elucidating the influence of varying the process parameters, such as print speed, spacing, and dimensions. An in-depth understanding of the bond quality between the prepregs and the printed polymers as well as the interlaminar fracture surfaces formed on the Mode-II fracture toughness values are established by developing an experimentally validated thermo-chemical finite element modeling framework.