Blends containing PVC and aramid (Ar) matrices were probed for their miscibility. In this respect, Ar chains were synthesized by aromatic diamine and diacid chloride in amide solvent. The Ar thus synthesized was characterized through Fourier transform infrared (FTIR) spectroscopy and molecular weight determination. Blend system Ar/PVC was investigated over a range of Ar/PVC ratios. Their mechanical profiles in terms of maximum stress, maximum strain, toughness, and initial moduli have been explored. Thermal properties and morphology of the blends were estimated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). A good correlation was observed between thermal, mechanical, and morphological properties of the blends. The presence of hydrogen bonding among polymers was evaluated through FTIR spectroscopy, which is believed to be responsible for the blend miscibility. Optimal thermal and mechanical profiles were depicted by the blend containing 40-wt% PVC in the Ar matrix.