Lipids, as naturally occurring biomolecules have emerged as promising carriers for delivering various therapeutic agents. However, only a few attempts have been made in terms of their applications as amphiphilic block copolymers for anticancer drug delivery. In this work, a biocompatible micellar drug delivery system with fatty acid-based polymer core and temperature-sensitive shell was developed. A series of amphiphilic block copolymers poly(vinyl stearate)/poly(vinyl laurate)-b-poly(N-vinylcaprolactam) (PVS/PVL-b-PNVCL) were synthesized via microwave-assisted reversible addition-fragmentation chain transfer polymerization in a controlled fashion. By varying the fatty acid type and hydrophilic/hydrophobic block lengths, the self-assembly behaviour of the block copolymer micelles proved to be highly tunable in terms of their morphology and particle size. Nile Red and hydrophobic anticancer drug doxorubicin (DOX) were effectively incorporated into the micelles, demonstrating high drug loading capacity, good serum stability, and temperature-dependent drug release characteristics of the polymeric micelles. In vitro studies using cell models revealed that blank PVS -b-PNVCL micelles are biocompatible with different cell lines, while DOX-loaded micelles were internalized into and accumulated in the cells, showing a high cytotoxic effect against HeLa cells. These findings suggest an opportunity for the development of safe and efficient lipid-based micellar system for smart drug delivery and cancer treatments.