The present study describes the microwave-assisted preparation and physicochemical characterization of an iron(II)–piperine coordination complex derived from piperine isolated from black pepper (Piper nigrum L.), followed by preliminary evaluation of its apoptosis-associated activity against MCF-7 breast cancer cells. Piperine was obtained from black pepper by microwave-assisted ethanolic extraction followed by alkaline purification, crystallization and recrystallization. The isolated piperine showed an Rf value of 0.61 and a melting point of 129 °C, with an isolation yield of 59.7%. The iron complex was prepared using piperine and anhydrous ferrous sulphate in a 2:1 ligand-to-metal molar ratio under microwave irradiation. The resulting reddish-brown Fe–O–piperine complex was obtained in 75.32% yield and showed a melting point of 131 °C. UV–visible spectroscopy showed a shift in the principal absorption maximum from approximately 343 nm for piperine to 399 nm for the iron complex. FT-IR analysis showed a carbonyl-region band near 1620 cm⁻¹ and a low-frequency band at approximately 553 cm⁻¹ assigned to Fe–O coordination. The ¹H and ¹³C NMR data retained the characteristic piperine framework while indicating changes in the electronic environment near the carbonyl group; the ¹³C carbonyl-related resonance was observed at approximately 171 ppm. Mass spectrometric analysis showed a high-mass species at approximately m/z 626.21, consistent with a species containing two piperine ligand units and iron. Annexin V-FITC/propidium iodide flow-cytometric analysis in MCF-7 cells showed apoptosis-associated changes after exposure to the complex at 10–80 µM, with total apoptosis in the displayed treatment profile ranging from 18.74% to 21.97%. These findings provide preliminary evidence that the Fe–O–piperine complex can alter the apoptotic profile of MCF-7 cells; however, the non-linear concentration response and the baseline apoptotic fraction observed in the control profile warrant confirmation using independent biological replicates, appropriate positive controls and mechanistic assays.