To selectively and sensitively determine the trace inorganic As species, As(III) and As(V), we developed a nanocomposite-coated microfluidic-based photocatalyst-assisted reduction device (PCARD) as a vapor generation (VG) device to couple high-performance liquid chromatography (HPLC) separation and inductively coupled plasma-mass spectrometry (ICPMS) detection. Au nanoparticles were deposited on TiO2 nanoparticles to strengthen the conversion efficiency of the nanocomposite photocatalytic reduction. The sensitivity for As was significantly enhanced by employing the nanocomposite photocatalyst and using prereduction and signal-enhancement reagents. Under the optimal operating conditions, the analytical detection limits (based on 3σ) of the proposed online HPLC/nanocomposite-coated microfluidic-based PCARD/ICPMS system for As(III) and As(V) were 0.23 and 0.34 μg·L-1, respectively. The results were validated using a certified reference material (NIST SRM 1643e) and groundwater sample analysis, indicating the good reliability and applicability of our proposed system for the determination of inorganic As species in natural fresh water.