The construction of complex molecules from readily available alcohols via C–C bond formation reactions is of great interest in organic synthesis. Silver‐coated Fe3O4 nanoparticles (Fe3O4@Ag) were prepared and used as magnetic catalyst for the chemoselective C–C cross‐coupling of benzyl alcohol and 1‐phenylethanol to form 1,3‐diphenylpropan‐1‐one or 1,3‐diphenylpropan‐1‐ol. This magnetically separable catalyst was also found to exhibit high catalytic activity in one‐pot, three‐component reaction of benzyl alcohol, 1‐phenylethanol and 3‐aminopyrazole for the synthesis of pharmaceutical skeleton pyrazolo[1,5‐a]pyrimidine. The catalytic system can be successfully reused 10 times with a small decrease of its catalytic performance. The catalyst shows extraordinary catalytic activity, high stability, good reusability, and wide applicability to diverse substrates.