A dual extraction based on solid phase extraction (SPE) and solidified floating organic drop microextraction (SFODME) was developed for As species in tea leaves and tea infusion by electrothermal vaporization inductively coupled plasma mass spectrometry, including total, suspended, soluble, organic and inorganic As as well as As(III) and As(V). In SPE step, titanium dioxide nanotubes were used for preconcentration of analytes and removal of sample matrix. Elution solution from SPE was employed for further preconcentration and separation of analytes with SFODME. Under optimal conditions, detection limits of this method were 0.046 and 0.072 pg mL(-1) with relative standard deviations of 6.3% and 5.8% for As (III) and As(V) (n = 9, c = 1.0 ng mL(-1)), respectively. A preconcentration factor of 500-fold was achieved for As(III) and As(V). This method was successfully applied for analysis of speciation of arsenic and its distribution in tea leaves, tea infusion and certified reference material of tea leaves. (C) 2016 Elsevier Ltd. All rights reserved.