Peapodlike Ni/Ni3S2 chains of about 30 nm in outer diameter, with Ni cores of 10–15 nm, can be synthesized by a sacrificial template route. The Ni3S2 shell exhibits paramagnetic properties with a mass susceptibility of χ ≈ 5 × 10−5 emu (gOe)−1, while the ferromagnetic Ni cores show a superparamagnetic behavior with a blocking temperature of TB ≈ 130 K. The shape anisotropy of the chainlike structure is determined as 5.0 × 104 J·m−3, which is larger than the bulk magnetocrystalline anisotropy by one order of magnitude. The demagnetization factor is determined as ΔN = 0.29. The sample provides an ideal structure for studying the magnetization reversal property by the chain-of-sphere model. The observations on the formation of the peapod structure verify a growth mechanism of the nanoscale Kirkendall effect. Based on the preparation of peapod chains, a series of nickel sulfide hollow chains with average diameters of 25, 50, and 100 nm are fabricated. In addition, the phase transition for hollow chains from Ni3S2 to NiS is studied.