Rapid gas-evaporation method is proposed and developed, which yields Si nanoparticles (SiNPs) in a few seconds at high yields of 20%–60% from inexpensive and safe bulk Si. Such rapid process is realized by heating the Si source to a temperature ≥2000 °C, much higher than the melting point of Si (1414 °C). The size of SiNPs is controlled at tens to hundreds nanometers simply by the Ar gas pressure during the evaporation process. Self-supporting films are fabricated simply by co-dispersion and filtration of the SiNPs and carbon nanotubes (CNTs) without using binders nor metal foils. The half-cell tests showed the improved performances of the SiNP-CNT composite films as anode when coated with graphitic carbon layer. Their performances are evaluated with various SiNP sizes and Si/CNT ratios systematically. The SiNP-CNT film with a Si/CNT mass ratio of 4 realizes the balanced film-based capacities of 618 mAh/gfilm, 230 mAh/cm3, and 0.644 mAh/cm2 with a moderate Si-based performance of 863 mAh/gSi at the 100th cycle.