Fused deposition modeling (FDM) printing of commercial and reinforced filaments is a proven and well-explored method for the enhancement of mechanical properties. However, little has hitherto been reported on the multi-material components, fused or laminated together into a single specimen by using the laminated object manufacturing (LOM) technique for sustainable/renewable polymers. TPU is one such durable and flexible, sustainable material exhibiting renewable and biocompatible properties that have been explored very less often in combination with the ABS polymer matrix in a single specimen, such as the LOM specimen. The current research work presents the LOM manufacturing of 3D-printed flexural specimens of two different, widely used polymers available viz. ABS and TPU and tested as per ASTM D790 standards. The specimens were made and laminated in three layers. They were grouped into two categories, namely ABS: TPU: ABS (ATA) and TPU: ABS: TPU (TAT), which are functionally graded, sandwiched structures of polymeric material. The investigation of the flexural properties, microscopic imaging, and porosity characteristics of the specimens was made for the above categories. The results of the study suggest that ATA-based samples held larger flexural strength than TAT laminated manufactured samples. A significant improvement in the peak elongation and break elongation of the samples was achieved and has shown a 187% increase in the break elongation. Similarly, for the TAT-based specimen, flexural strength was improved significantly from approximately 6.8 MPa to 13 MPa, which represents a nearly 92% increase in the flexural strength. The morphological testing using Tool Maker’s microscopic analysis and porosity analysis has supported the observed trends of mechanical behavior of ATA and TAT samples.