In tris(tert-butyl)phosphine selenide, C(12)H(27)PSe, all the methyl ligands are disordered over two sites in the ratio 70/30. The molecule displays crystallographic C(3) symmetry. The bond angles at the P atom are distorted tetrahedral [C--P--C 110.02 (5) degrees and Se==P--C 108.91 (5) degrees ]. The P--C and P==Se bond lengths are 1.908 (1) and 2.1326 (6) A, respectively. A comparison of the structural data of the complete series of tris(tert-butyl)phosphine chalcogenides ((t)Bu(3)PO, (t)Bu(3)PS, (t)Bu(3)PSe and (t)Bu(3)PTe) with the corresponding data of other phosphine chalcogenides substituted by smaller organic groups shows the great influence of the bulky tert-butyl ligands.