Double perovskites without lead element have attracted great attention in recent years. Further increasing the photoluminescence quantum yield of lead-free double perovskites is necessary for their potential applications. In this work, Na+ doped Cs2SnI6 nanocrystals were synthesized by hot injection method. It was displayed that all the NCs have uniform hexagonal shape with good crystallization. Energy dispersing spectroscopy and X-ray photoelectron spectroscopy proves the Na+ ions were doped in the lattice of perovskite structure. The photoluminescence intensity of doped NCs is increased by 2.7-fold than that of pure NCs. A maximum photoluminescence quantum yield of 72% is obtained. The luminous mechanism was investigated by femtosecond transient absorption spectrum and a self-trap emission was proved by the observation of ground state bleaching and photo-induced absorption signals.