The Slave craton underwent widespread extension during the Paleoproterozoic. The East Arm basin of Great Slave Lake formed during this period and preserves a protracted record of sedimentation and volcanism in the southeastern Slave craton. Within the East Arm basin package, the Union Island Group represents voluminous mafic volcanism with subordinate sedimentary strata. We report the first high precision U–Pb zircon and baddeleyite dates for the Union Island Group; 2045.8 ± 1.0 Ma for a volcaniclastic unit from the lower basalt formation and 2042.7 ± 3.0 Ma for a diabase intrusion within volcaniclastic horizons in the lower basalt formation. We fundamentally revise the lower basin stratigraphy and demonstrate that the Union Island Group is the oldest identified supracrustal package in the East Arm basin, ∼120 Myr older than previously thought. This revised stratigraphy is supported by detrital zircon provenance age distribution in two Union Island Group sedimentary samples, which is dominated by 2.76–2.56 Ga ages, reflecting prominent input from the local Archean Slave basement.The Union Island Group contains two geochemically distinct mafic volcanic packages. The lower basalt package is predominantly alkaline, characterized by an OIB-like chemical signature with high and variable incompatible element contents (108–438 ppm Zr, 13–62 ppm Nb). In contrast, the upper basalt package is tholeiitic, contains much lower and uniform incompatible element contents (83–101 ppm Zr, 2–4 ppm Nb), and has an E-MORB-like chemical signature. Both packages display overlapping, depleted time-integrated εNd(i) values (+1.1 to +3.2). Petrological modeling suggests the lower package originated as OIB-like melts from the asthenosphere that interacted with a depleted reservoir; the upper package was produced by larger degree of partial melting of a similar mantle source, in addition to possible lithospheric input. The petrogenesis established in this study is consistent with a passive continental rift origin for the Union Island Group magmatism and is further supported by geochemical similarities with Proterozoic and Phanerozoic rift successions. We therefore propose that the 2046 Ma Union Island Group represents an incipient rift basin sequence formed during Paleoproterozoic extension that marked the initial breakup of the southern margin of the Slave craton from a pre-Laurentia supercontinent.