Well-defined mid-chain functional macrophotoinitiator of poly(epsilon-caprolactone) (PCL-PI-PCL) was synthesized by combination of ring-opening polymerization (ROP) and click chemistry strategy. Dibromo functional photoinitiator (Br-PI-Br) was prepared by the condensation of 2-bromopropanoyl bromide with 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl propan-1-one (PI). Subsequently, terminal bromo groups in Br-PI-Br were converted to azido groups to form diazido functional photoinitiator (N-3-PI-N-3) using NaN3. Well-defined precursor alkyne-functionalized PCL (alkyne-PCL) was prepared by ROP of epsilon-CL in the presence of propargyl alcohol as the initiator and stannous-2-ethylhexanoate (Sn(Oct)2) as the catalyst. Finally, the alkyne-functionalized PCL was coupled with N-3-PI-N-3 with high efficiency by click chemistry. The spectroscopic studies showed that low-polydispersity PCL with desired photoinitiator functionality in the middle of the chain was obtained.