The breakup of the supercontinent Rodinia and development of the western Laurentian rifted margin are in part recorded by Neoproterozoic to mid-Paleozoic igneous and sedimentary rock successions in the Canadian Cordillera. New bedrock mapping and volcanic facies analysis of Early Ordovician mafic rocks assigned to the Menzie Creek Formation in central Yukon allow reconstruction of the depositional environment during the volcanic eruptions, whole-rock geochemical data constrain the melting depth and crust-mantle source regions of the igneous rocks within the study area, and zircon U-Pb age studies provide determination of the precise timing of submarine eruptions. Menzie Creek Formation volcanic rocks are interlayered with continental slope strata and show lithofacies consistent with those of modern seamount systems. Representative seamount facies contain several kilometers of hyaloclastite breccia and pillow basalt with rare sedimentary rocks. Menzie Creek Formation seamounts form a linear array parallel to the Twopete fault, an ancient extensional or strike-slip fault that localized magmatism along the nascent western Laurentian margin. Zircon grains from two volcanic successions yielded high-precision chemical abrasion–thermal ionization mass spectrometry (CA-TIMS) dates of ca. 484 Ma (Tremadocian), which are interpreted as the age of eruption. Menzie Creek Formation rocks are alkali basalt and have oceanic-island basalt–like geochemical compositions. The whole-rock trace element and Nd-Hf isotope compositions are consistent with the partial melting of subcontinental lithospheric mantle at ~75–100 km depth. Post-rift, Early Ordovician seamounts in central Yukon record punctuated eruptive activity along a rift-related fault, the separation of a continental fragment from western Laurentia, or the oblique post-breakup kinematics from the counterclockwise rotation of Laurentia that facilitated local extension in the passive margin.