Polypropylene/molybdenum disulfied (PP/MoS2) and Polypropylene/hexagonal boron nitride (PP/hBN) nanocomposites with varying concentration (0–6 wt %) were fabricated via in situ polymerization using two-dimensional (2D)-nanosheet/MgCl2-supported Ti-based Ziegler–Natta catalysts, which was prepared through a novel coagglomeration method. For catalyst preparation and interfacial interaction, MoS2 and hBN were modified with octadecylamine (ODA) and octyltriethoxysilane (OTES), respectively. Compared with those of pristine PP, thermal stability of composites was 70 °C higher and also tensile strength and Young’s modulus of the composites were up to 35% and 60% higher (even at small filler contents), respectively. The alkyl-modified 2D nanofillers were characterized by strong interfacial interactions between the nanofiller and the polymer matrix. The coagglomeration method employed in this work allows easy introduction and content manipulation of various 2D-nanosheets for the preparation of 2D-nanosheet/MgCl2-supported Ti-based Ziegler–Natta catalysts.