In this study, a new approach for Laser-induced Breakdown Spectroscopy (LIBS) with gold nanofilm (NF) deposited on sample surface was carried out by using femtosecond laser. Different materials including metallic sample, semiconductor sample and dielectric sample were tested. Strong emission enhancement was obtained on SiO2, ceramic and Si sample. It was found that different lines in ceramic sample had different enhancement effect, which was probably related to concentration of different substances in ceramic. The enhancement effect was found to weaken with the increase of laser fluence. Enhancement factors of about 14 for SiO2, 5 for ceramic and 3 for Si sample were achieved at laser fluence of 3.3 J/cm(2), which decreased to 9 for SiO2, 3 for ceramic and 1.5 for Si sample at laser fluence of 8.8 J/cm(2). The mechanism of nanofilm-enhanced LIBS (NFELIBS) was localized surface plasmon resonance, which could change the dominant photon ionization process of sample.