The influence of the surfactants on the morphologies of trigonal selenium (t-Se) submicrostructures was studied in a two-step microfluidic system, which is composed of a glass microchip for preparing spherical amorphous selenium (a-Se) colloids coupled with a poly(methyl methacrylate) microchip for transferring a-Se into its t-Se seeds under sonication. The selenious acid containing surfactants and hydrazine solutions were delivered through the two-inlets of the glass microfluidic chip. Submicro-rods, -wires as well as -tubes of t-Se were obtained by simply varying the coexisted surfactants. The as-synthesized products were characterized by powder X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). (C) 2009 Elsevier Ltd. All rights reserved.