The significance of rheology in the context of bio three-dimensional (3D) printing lies in its impact on the printing behavior, which shapes material flow and the layer-by-layer stacking process. The objective of this study is to evaluate the rheological and printing behaviors of polycaprolactone (PCL) and dimethyl sulfone (DMSO2) composites. The rheological properties were examined using a rotational rheometer, employing a frequency sweep test. Simultaneously, the printing behavior was investigated using a material extrusion 3D printer, encompassing varying printing temperatures and pressures. Across the temperature range of 120-140 °C, both PCL and PCL/DMSO2 composites demonstrated liquid-like behavior, with a higher loss modulus than storage modulus. This behavior exhibited shear-thinning characteristics. The addition of DMSO2 10, 20, and 30 wt% into the PCL matrix reduced a zero-shear viscosity of 33, 46, and 74% compared to PCL, respectively. The materials exhibited extrusion velocities spanning from 0.0850 to 6.58 mm/s, with velocity being governed by the reciprocal of viscosity. A significant alteration in viscosity by temperature change directly led to a pronounced fluctuation in extrusion velocity. Extrusion velocities below 0.21 mm/s led to the production of unstable printed lines. The presence of distinct viscosities altered extrusion velocity, flow rate, and strut diameter. This phenomenon allowed the categorization of pore shape into three zones: irregular, normal, and no-pore zones. It underscored the importance of comprehending the rheological aspects of biomaterials in enhancing the overall quality of bio-scaffolds during the 3D printing process.