Microelectroforming is a specialized electroplating process to prepare functional metallic microstructures. However, the formability of microelectroforming is usually restricted by the limited mass transfer in high-aspect-ratio microcavities of molds. This paper presents a simple and reliable method utilizing silver (Ag)-coated polydimethylsiloxane (PDMS) molds with controllable wettability to enhance the formability of microelectroforming. The surfaces of these molds exhibited reversible water contact angles ranging from 4° to 151° realized through ultraviolet irradiation and heat treatment. The hydrophilicity of the PDMS molds facilitated liquid-phase mass transfer, contributing to the fabrication of complete and defect-free nickel microstructures with high aspect ratios. Subsequently, the hydrophobic PDMS molds reduced the interfacial adhesion between these molds and nickel microstructures, which was beneficial for perfect demolding. Nickel microstructures with an aspect ratio of 10 can be achieved by using the PDMS molds, which significantly enhance the formability of microelectroforming. This method provides a potential method to prepare high-aspect-ratio metallic microstructures.