Accessing a facile pathway to prepare polyolefin-polar block copolymers with low dispersity and high control remains a challenge due to the distinct polymerization pathways of the composing blocks. This study utilized the polyolefin active ester exchange, the PACE approach, as a viable solution. The PACE approach, using palladium-catalyst-based coordination-insertion polymerization, was combined with SARA ATRP (supplemental activator/reducing agent atom transfer radical polymerization). A single-chain-end active ester functionalized polyethylene (PE) was produced from an α-diimine Pd(II) hexafluoroisopropyl ester chelate complex, which facilitated a living polymerization of ethylene. Transesterification with 2-hydroxyethyl α-bromoisobutyrate (HOBIB) or 2-hydroxyethyl α-bromoisobutyramide (HOBIBA) formed α-bromoisobutyrate or α-bromoisobutyramide chain-end-functionalized polyethylene. The approach resulted in controlled synthesis of polymers with low dispersity (