Heavy-section link-chains are increasingly required to satisfy industrial demands of shipping, lifting, and mining machinery. In this study, the hardenability of link-chain steels with different Si contents was investigated using end-quench tests. The microstructures of the end-quenched specimens were examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mechanical properties were investigated by tension tests and impact tests. The effect of the Si content on the phase-transformation temperature during cooling was analyzed by differential scanning calorimetry. It was found that increasing the Si content from 0.24 to 0.74% led to a significant increase in hardenability; the ideal diameter (i.e., the diameter of given steel that would produce 50% martensite at the center when quenched in a hypothetical quenching medium that reduces the surface temperature of the heated steel to the bath temperature in zero time) increased from 187 to 248 mm. Si enhances the hardenability of link-chain steel by affecting its phase-transition behaviors during cooling, including suppressing ferrite formation, inhibiting carbide precipitation, and lowering the temperature of maximum transformation of bainite. The suggested Si content is 0.70-0.75% to produce link-chain steel with high hardenability and good mechanical properties.