Surface states in III-V semiconductor materials have detrimental effects on their optical and electronic properties, and the passivation of GaAs surface has become of longstanding interest. Here, we demonstrated a two-step process to greatly reduce surface states of GaAs (0 01) by a combination of Hg2Cl2 and alkanethiol. Firstly, uniformly distributed Hg2Cl2 nanoplates with a size around 200 nm were deposited on GaAs surface by the incubation of the etched wafer into the mercury (II) chloride solution, without the need of a reducing agent. Secondly, hexadecanethiol (HDT) molecules were assembled on the Hg2Cl2-GaAs hybrid surface, which decreases the density of surface states through electron transfer processes. Noticeably, after such two steps, a significant enhancement of photoluminescence (PL) signal was noted. It may be due to the fact that components of As2O3 and As-0 which are identified as major sources of the surface states are reduced considerably, or even disappear. Chemical state changes of mercury species are expected to play a key role in achieving the surface passivation. Obtained hybrid GaAs materials with considerably improved photonic signals open a new avenue for the fabrication of electronic and optoelectronic devices.