Macroscopic and molecular techniques such as differential scanning calorimetry (DSC) and electron spin resonance (ESR), respectively, were used to characterize both structure and dynamics of liposomes built up with dioleoyltrimethylammonium propane (DOTAP) and dioleoylphosphatidylethanolamine (DOPE) lipids. These liposomes are good candidates to act as molecular carriers in cancer therapy, such as, for instance, boron neutron capture therapy (BNCT). DSC revealed that neither T-m nor DeltaH(m) of the gel-liquid crystal phase transition depended on the presence of relatively concentrated exogenous molecules as they are the n-DSA and n-DPC spin probes used in this work. The results suggested that the structure and the internal dynamics of the liposomes did no change after small loading of the paramagnetic probes. This was proved at a molecular level by the computer analysis of the ESR spectra of the above probes, which revealed discontinuities of the motional parameters (correlation times, tau(perpendicular to) and tau(parallel to), and order parameter S-20) in the same range of temperatures of the endothermic events observed by DSC on probe-free liposomes. A dependence of tau(perpendicular to), tau(parallel to), and S-20 on the localization of the probe was found, and the activation energies for the motion were consistent with the mobility of the domains sensed by the different probes. The results reported in this work may be considered as a useful basis for the characterization of both plain and loaded liposomes when these aggregates are used as drug carriers.