This work focuses on the study of the microstructure and magnetic properties of nanocrystalline powders of Sm4ZrFe33, prepared by high‐energy ball milling. The Sm4ZrFe33 compound adopts a monoclinic structure (space group Cm). Upon annealing, these Sm4ZrFe33 samples exhibit notable variations in their extrinsic magnetic properties, closely linked to temperature fluctuations. The investigation delves into the correlation between morphology, grain size and magnetic characteristics. A significant enhancement in coercivity (Hc), remanent magnetization (Mr), and maximum energy product ((BH)max) is observed, primarily attributed to the finer grain structure present in the samples. Particularly noteworthy, among all annealed specimens, the nanocrystalline Sm4ZrFe33 compound annealed at a temperature of Ta = 973 K demonstrates the most promising magnetic properties. This specimen exhibits a coercivity Hc of 18 500 Oe, remanent magnetization (Mr) of 58 emu g−1, maximum energy product ((BH)max) of 5.18 MGOe, Curie temperature (TC) of ≈804 K, and magnetic anisotropy field (Ha) of 115 980 Oe. These research findings pave the way for future investigations and applications in the realm of permanent magnets, spintronic devices, and magnetic recording, utilizing nanocrystalline alloys based on the Sm4ZrFe33 compound.