Context. Young, close stars are ideal targets for searching planets using the direct imaging technique. The determination of stellar parameters is crucial for the interpretation of imaging survey results, particularly since the luminosity of substellar objects has a strong dependence on system age. Aims: 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 (age, distance, and mass) of the stars in our sample. To improve target age determinations, we compiled and analyzed a complete set of age diagnostics. Methods: We measured spectroscopic parameters and age diagnostics using dedicated observations acquired with FEROS and CORALIE spectrographs at La Silla Observatory. We also made extensive use of archival spectroscopic data and the results that are available in the literature. Additionally, we exploited photometric time-series, which are available in ASAS and Super-WASP archives, to derive a rotational period for a large fraction of our program stars. Results: 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. The median distance and age of our program stars are 64 pc and 100 Myr, respectively. Nearly all the stars have masses between 0.70 and 1.50 M⊙, with a median value of 1.01 M⊙. The typical metallicity is close to solar with a dispersion that is smaller than that of samples usually observed in radial velocity surveys. Several stars are confirmed or proposed here to be members of close young moving groups. Eight spectroscopic binaries are identified. Based on observations collected at La Silla and Paranal Observatory, ESO (Chile) using FEROS, HARPS, and NaCo; with the CORALIE echelle spectrograph mounted on the 1.2 m Swiss telescope at La Silla Observatory; and on the All Sky Automated Survey (ASAS) photometric data. Tables 1-4, 6, 8 and Appendices are available in electronic form at http://www.aanda.orgTables 9-12 and D.1 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/573/A126