Young, close stars are ideal targets for searching planets using the direct imaging technique. We have conducted a large program with NaCo at the VLT to search for planets and brown dwarfs in wide orbits around 86 stars. A large fraction of the targets observed with NaCo were poorly investigated in the literature. We performed a study to characterize the fundamental properties of the stars in our sample. To improve target age determinations, we compiled and analyzed a complete set of age diagnostics. We measured spectroscopic parameters and age diagnostics using dedicated observations acquired with FEROS and CORALIE spectrographs at La Silla Observatory. We provided updated characterization of all the targets observed in the VLT NaCo Large program, a survey designed to probe the occurrence of exoplanets and brown dwarfs in wide orbits. Several stars are confirmed or proposed here to be members of close young moving groups. Eight spectroscopic binaries are identified.