This study contributes to an understanding of how different polymeric structures, in special triblock copolymers can interact with the lipid bilayer. To study the phospholipid-copolymer vesicles system, we report the effect of two amphipathic triblock copolymers of the type BAB, i.e., hydrophobic-hydrophilic-hydrophobic triblock copolymers arranged as poly(epsilon-caprolactone)poly(ethylene oxide)-poly(epsilon-caprolactone) (PCLn-PEOm-PCLn), where n = 12 and m =45 for COP1 and n=16 and m = 104 for COP2, on the dynamic and structural properties of dipalmitoyl-phosphatidylcholine (DPPC) large unilamellar vesicles (LUVs). The interaction between the copolymers and DPPC LUVs was evaluated by means of several techniques: (a) Photographs of the dispersion for evaluation of colloidal stability; (b)Thermotropic behavior from generalized polarization of Laurdan and fluorescence anisotropy of DPH (c) Main phase transition temperature determination; (d) Order parameters and limiting anisotropy by time-resolved fluorescence anisotropy measurements; (e) Water outflow through the lipid bilayer and (f) Calcein release from DPPC LUVs. Steady-state fluorescence measurements as a function of temperature show a typical behavior. Laurdan and DPH are fluorescent probes that sense the interface and the inner part of the bilayer, respectively. Both copolymers increase the Tm value of DPPC LUVs sensed by DPH, i.e., in the inner part of the bilayer. On the contrary, only COP2 had an effect on increasing the Tm value at the interface of the bilayer. At low temperature, in the gel phase, the presence of the copolymers produced a slight decrease in generalized polarization of Laurdan sensed in the interface of the lipid bilayer, but in the liquid-crystalline phase it produced an increase. In contrast, the order parameters obtained from time-resolved fluorescence anisotropy of DPH show an increase in the presence of the copolymers in the gel phase, but a decrease in the liquid-crystalline phase. COP2 produces a greater effect than COP1 in decreasing the water outflow through DPPC LUVs in the same concentration range. Furthermore, calcein release was decreased to a minimum at low copolymer concentration; however, at high concentration, release factor percentage (RF%) increased slightly without reaching the values obtained in the absence of copolymers. Therefore, the copolymer concentrations studied decrease the calcein release from the liposome. (C) 2016 Elsevier B.V. All rights reserved.