With the increasing demand for electronic products, the amount of multilayer ceramic capacitor (MLCC) waste has also increased. Recycling technology has recently gained attention because it can simultaneously address raw material supply and waste disposal issues. However, research on recovering valuable metals from MLCCs and converting the recovered metals into high-value-added materials remains insufficient. Herein, we describe an electrospinning (E-spinning) process to recover nickel from MLCCs and modulate the morphology of the recovered nickel oxide particles. The nickel oxalate powder was recovered using organic acid leaching and precipitation. Nickel oxide nanoparticles were prepared via heat treatment and ultrasonic milling. A mixture of nickel oxide particles and polyvinylpyrrolidone (PVP) was used as the E-spinning solution. A PVP/NiO nanowire composite was fabricated via Espinning, and a nickel oxide nanowire with a network structure was manufactured through calcination. The nanowire diameters and morphologies are discussed based on the nickel oxide content in the E-spinning solution.