The B+→D+sD−sK+ decay is observed for the first time using proton-proton collision data collected by the LHCb detector at center-of-mass energies of 7, 8, and 13 TeV, corresponding to an integrated luminosity of 9 fb−1. Its branching fraction relative to that of the B+→D+D−K+ decay is measured to be B(B+→D+sD−sK+)B(B+→D+D−K+)=0.525±0.033±0.027±0.034, where the first uncertainty is statistical, the second systematic, and the third is due to the uncertainties on the branching fractions of the D±s→K∓K±π± and D±→K∓π±π± decays. This measurement fills an experimental gap in the knowledge of the family of Cabibbo-favored ¯b→¯cc¯s transitions and opens the path for unique studies of spectroscopy in future.Received 10 November 2022Accepted 8 February 2023DOI:https://doi.org/10.1103/PhysRevD.108.034012Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI. Funded by SCOAP3.© 2023 CERN, for the LHCb CollaborationPhysics Subject Headings (PhySH)Research AreasMultiquark bound statesParticle decaysQuantum chromodynamicsParticles & Fields