A covalently immobilized calix[7]hydroquinone monolayer was used as the host matrix to synthesize metallic NPs using an in situ redox process. The characteristics of different metallic ions that affect the synthesis process were studied. Metallic ions with less charges, lower oxidation state in the reaction, and higher standard redox potential provided better yield. Bimetallic NPs with a core shell structure were synthesized by a sequential deposition of different metals on the same monolayer. The process was applied to form a layer of immobilized NPs on flat and curved surfaces. The ability to synthesize and immobilize well-controlled NPs on different surfaces has promising applications in decoration of irregular surfaces of miniaturized, three-dimensional objects.