Argon cluster sputtering of an organic multilayer reference material consisting of two organic components, 4,4′‐bis[N‐(1‐naphthyl‐1‐)‐N‐phenyl‐ amino]‐biphenyl (NPB) and aluminium tris‐(8‐hydroxyquinolate) (Alq3), materials commonly used in organic light‐emitting diodes industry, was carried out using time‐of‐flight SIMS in dual beam mode. The sample used in this study consists of a ~400‐nm‐thick NPB matrix with 3‐nm marker layers of Alq3 at depth of ~50, 100, 200 and 300 nm. Argon cluster sputtering provides a constant sputter yield throughout the depth profiles, and the sputter yield volumes and depth resolution are presented for Ar‐cluster sizes of 630, 820, 1000, 1250 and 1660 atoms at a kinetic energy of 2.5 keV. The effect of cluster size in this material and over this range is shown to be negligible. © 2014 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd.