Femtosecond (fs) and nanosecond (ns) laser pulses have their own advantages and disadvantages in laser-induced breakdown spectroscopy (LIBS). This paper investigated fs + ns (FN) dual-pulse (DP) LIBS, utilizing the respective advantages of two laser pulses in LIBS. Compared to traditional single ns LIBS, applying a smaller energy fs pulse could effectively improve the LIBS emission. Firstly, this study discussed the spectra of FN DP LIBS with overlapping pulse time—that is, the FN DP inter-pulse delay (DID) was 0 μs. The results showed that the spectra were increased to three times that of a single ns LIBS. Subsequently, the DID between the two pulses was optimized. The results showed that as the DID between the two pulses increased, the spectral emission first increased and then decreased, ultimately remaining unchanged. The optimized DID was approximately 2 μs. Finally, using this optimized DID, the variation of spectral intensity with ns laser energy was discussed in DP LIBS. The spectral enhancement ratio increased from 3 with 0 μs DID to 6 with 2 μs DID. The investigation provides a reference in the application of FN DP LIBS element analysis.