Luminescence of Eu3+ in stoichiometric host luminescent crystal Na5Eu(WO4)4 has been studied under low temperature 20-300 K and hydrostatic high pressure 0 - 10 GPa using a diamon anvil high pressure and low temperature microspectroscopic system. We report for the pressure shift rates of spectral lines, energy levels and crystal field parameters of Eu3+ under low temperature. These pressure shift rates vary directly with temperature, and the experiment shows that the effects of temperature or pressure on the spectral lines of Eu3+ are not independent like that of R1 and R2 spectral line in ruby. According to crystal field theory, we have suggested a simplified method to derive the relations between energy levels and crystal parameters. The pressure shift rates of crystal parameters at low temperature(△Bkg/△p)T have been determined by fitting with the experimental spectral data.