Acrylate-based photo-cross-linked poly­(ε-caprolactone) (PCL) tends to show low elongation and strength. Incorporation of osteo-inductive hydroxyapatite (HAp) further enhances this effect, which limits its applicability in bone tissue engineering. To overcome this, the thiol–ene click reaction is introduced for the first time in order to photo-cross-link PCL composites with 0, 10, 20, and 30 wt % HAp nanoparticles. It is demonstrated that the elongation at break and ultimate strength increase 10- and 2-fold, respectively, when the photopolymerization mechanism is shifted from a radical chain-growth (i.e., acrylate cross-linking) toward a radical step-growth polymerization (i.e., thiol–ene cross-linking). Additionally, it is illustrated that osteoblasts can attach to and proliferate on the surface of the photo-cross-linked PCL-HAp composites. Finally, the incorporation of HAp nanoparticles is shown to reduce the ALP activity of osteoblasts. Overall, thiol–ene cross-linked PCL-HAp composites can be considered as promising potential materials for bone tissue engineering.