This study investigates the synergistic integration of silk protein and polycaprolactone (PCL) in blends derived from distinct solvents, with the primary aim of enhancing the biocompatibility of PCL and preparing a mixture suitable for 3D printing of functional scaffolds. The research explores the interaction between silk protein and PCL, revealing crucial insights into their morphological transformations and structural changes. The formation of silk protein particles in the mixture with PCL has been observed. These particles exert a profound influence on the spherulitic structure of PCL, with significant changes occurring at various concentrations. At low concentrations of silk protein, a ring-banded structure emerges, reshaping the traditional spherulites associated with PCL. As the concentration of silk protein increases in the mixture, there is a gradual disappearance of spherulites, ultimately leading to the formation of a pit-patterned surface in the case of a majority contribution of silk protein in the blend. These observations underscore the influence of silk protein in modulating the surface properties of PCL blends, presenting new opportunities for tailoring material characteristics in 3D printing applications for tissue engineering.