Herein, a straightforward method for the synthesis of 2,5-disubstituted selenophenes via [2+2+1] cyclization of easily accessible terminal alkynes and elemental selenium has been developed. This reaction features high atom- and step-economy, excellent regioselectivity, good functional group tolerance and the use of stable and non-toxic selenium as a selenium source. A series of control experiments suggests that the reaction might undergo Glaser coupling reaction of two molecules of alkynes, followed by insertion of H2Se and subsequent cyclization. Moreover, the newly formed products can be further converted to diverse conjugated selenophene-based derivatives, demonstrating their potential applications in organic synthesis and materials science.