Heavy metal pollution is one of the main problems in water pollution, which is harmful to humans. Surface-enhanced laser-induced breakdown spectroscopy (SENLIBS) has been applied to detect trace amounts of heavy metal elements in aqueous solution; however, it is still a big challenge to explore the relationship between the LIBS detection sensitivity and the substrate's physical properties. In this work, four typical substrates, zinc (Zn), magnesium alloy (Mg), nickel (Ni), and silicon (Si), were compared; and the mechanism of spectral enhancement by different substrates in SENLIBS was investigated. The results indicated that the limit of detection (LoD) of heavy metal elements on different substrates is positively proportional to the boiling of the substrate. That is mainly because a higher plasma excitation temperature and electron density are obtained, leading to more intense collision between particles. The signal enhancement is associated with the lower boiling point of the substrate (corresponding to a lower ablation threshold and higher ablation quantity from the substrate). As a result, the best LoD was 0.0011 mg/L for chromium (Cr) and 0.004 mg/L for lead (Pb) on an optimal Zn substrate, respectively. The LoDs were sufficiently low to meet the drinking water sanitation standard. These results showed that the detection sensitivity of heavy metal elements in aqueous solution can be improved by choosing a substrate with a lower boiling point in SENLIBS.