In this work, an effort has been made for multimaterial three-dimensional printing of functionally graded prototypes of polylactic acid matrix (tensile specimens as per ASTM D638 type IV) followed by characterization of mechanical and surface properties. The work is an extension of previous reported studies on twin-screw extrusion process for the preparation of multimaterial wires as feedstock filaments in possible three-dimensional printing applications. The results of the study suggest that the highest peak strength (46.28 MPa) and break strength (41.65 MPa) was obtained for multimaterial three-dimensional printed samples at infill density 100%, infill angle 45°, and infill speed of 90 mm/s on commercial open source fused deposition modeling setup. Further surface hardness measurements performed on two extreme surfaces (top surface comprising magnetite (Fe3O4)-reinforced polylactic acid and bottom with polylactic acid without any reinforcement) revealed that the hardness for the bottom layer was more than the hardness for the top layer. From fractured surface analysis (using photomicrographs), it has been observed that the three-dimensional printed samples with low infill density resulted into more void formation due to which the performance while mechanical testing was poor in comparison to samples printed with higher infill density. The results are also supported by rendered images of photomicrographs, which revealed that high roughness value of samples printed with low infill density was also one of the reasons for poor mechanical performance of multimaterial three-dimensional printed functionally graded prototypes.