The thermal properties and alignment of crystallinity of materials in thin films play crucial roles in the performance and reliability of various devices, especially in the fields of electronics, materials science, and engineering. The slight variations in the molecular packing of the active layer can make considerable differences in the optical and thermal properties. Herein, we aim to investigate the tuning of the physical properties of a blended thin film of n-type small organic molecules of perylene-3,4,9,10-tetracarboxylic acid (PTCA-SMs) with the mixing of the p-type polymer poly(3-hexylthiophene) (P3HT). The resulting thin films exhibit an enhanced surface crystallinity compared to the pristine material, leading to the formation of long crystallites, and these crystallites are thermally stable in the solid state, as confirmed by X-ray diffraction (XRD), atomic force microscopy (AFM), and thermal analysis using variable-temperature spectroscopic ellipsometry (VTSE) and differential scanning calorimetry (DSC). We believe that the crystalline structure of the obtained P3HT/PTCA-SMs blends is a combination of edge-on and face-on orientations, which enable the potential use of this material as an active layer in organic electronics.