In this work, we present the analysis and discussion of the first 0.6-5.2 μm spectra of Pluto at four different longitudes obtained with the James Webb Space Telescope (JWST). These spectra were acquired during year 1 of operations of JWST under the GTO-1 program #1191, led by J. Stansberry. The high-resolution (R~2700), high-sensitivity combination of Webb/NIRSPEC using G140H, G235H, and G395H enables the robust detection of a diverse set of solid species. Some of these species, CH4, β-N2, CO and and C2H6 were previously known or suggested while others are now detected for the first time, including CH3D (deuterated methane) and CO2. The spectra also show expected absorptions by CH4 gas from Pluto's atmosphere, and for the first time, fluorescent emissions due to CH4, CO and CH3D gas at 3.3, 4.7 and 4.54 μm respectively