We present echelle spectrophotometry of the Galactic HII region S 311. The data have been taken with the Very Large Telescope Ultraviolet-Visual Echelle Spectrograph in the 3100-10400 Årange. We have measured the intensities of 263 emission lines; 178 are permitted lines of H0, D0 (deuterium), He0, C0, C+, N0, N+, O0, O+, S+, Si0, Si+, Ar0 and Fe0; some of them are produced by recombination and others mainly by fluorescence. Physical conditions have been derived using different continuum- and line-intensity ratios. We have derived He+, C++ and O++ ionic abundances from pure recombination lines as well as abundances from collisionally excited lines for a large number of ions of different elements. We have obtained consistent estimations of t2 applying different methods. We have found that the temperature fluctuations paradigm is consistent with the Te(HeI) versus Te(HI) relation for HII regions, in contrast with what has been found for planetary nebulae. We report the detection of deuterium Balmer lines up to Dδ in the blue wings of the hydrogen lines, whose excitation mechanism seems to be continuum fluorescence.