Mass fractions of Sn and In were determined in sixteen geological reference materials including basaltic/mafic (BCR‐2, BE‐N, BHVO‐1, BHVO‐2, BIR‐1, OKUM, W‐2, WS‐E), ultramafic (DTS‐2b, MUH‐1, PCC‐1, UB‐N) and felsic/sedimentary reference materials (AGV‐2, JA‐1, SdAR‐M2, SdAR‐H1). Extensive digestion and ion exchange separation tests were carried out in order to provide high yields (> 90% for Sn, > 85% for In), low total procedural blanks (~ 1 ng for Sn, < 3 pg for In) and low analytical uncertainties for the elements of interest in a variety of silicate sample matrices. Replicate analyses (n = 2–13) of Sn–In mass fractions gave combined measurement uncertainties (2u) that were generally < 3% and in agreement with literature data, where available. We present the first high‐precision In data for reference materials OKUM (32.1 ± 1.5 ng g−1), DTS‐2b (2.03 ± 0.25 ng g−1), MUH‐1 (6.44 ± 0.30 ng g−1) and PCC‐1 (3.55 ± 0.35 ng g−1) as well as the first Sn data for MUH‐1 (0.057 ± 0.010 μg g−1) and DTS‐2b (0.623 ± 0.018 μg g−1).