We report on a new available strategy for fabricating CdS QD–polymer hybrids networks with enhanced photoluminescence (PL). Firstly, we synthesized a series of versatile polymeric ligands for the preparation of nanocrystals by catalytic chain transfer polymerization (CCTP) and radical addition–fragmentation polymerization (RAFT) methods. With these versatile polymeric ligands containing a large number of anchors and double bond functional groups, CdS QD–polymer networks were fabricated by the intramolecular cross-linking interaction between the polymeric ligands on the surfaces of each CdS nanocrystal. The as-prepared QD–polymers herein exhibit stable and highly enhanced PL properties relative to their PL before cross-linking. In addition, by measuring the changes of PL intensity, we found the PL intensity of QD–polymers demonstrated remarkable enhancement after 7 months. Related mechanisms were briefly discussed.