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The technique of H Rydberg atom photofragment translational spectroscopy has been applied to a high resolution study of the primary photochemistry of methanethiol (CH3SH) following excitation at a wide range of wavelengths in the near ultraviolet. In accord with previous studies of this molecule, excitation within its first (1 1A‘-X 1A’) absorption continuum is shown to result in S–H bond fission. Spectral analysis yields a refined value for the bond dissociation energy: D00(CH3S–H)=30 250±100 cm-1. The resulting CH3S(X) fragments are deduced to carry only modest vibrational excitation, distributed specifically in the ν3 (C–S stretching) mode and in one other mode having a wave number of ∼1040 cm-1. We associate this latter mode with bending of the CH3 moiety in the plane containing the C and S nuclei and the lobe of the unpaired electron which was originally involved in the S–H bond. Decreasing the excitation wavelength (while remaining within the first absorption continuum) results in an increase in both the vibrational and rotational excitation of the CH3S(X) fragments, but a decrease in the relative yield of the upper (2E1/2) spin–orbit component. Excitation at still shorter excitation wavelengths accesses the second (2 1A‘-X 1A’) absorption band of CH3SH. The CH3S fragments resulting from S–H bond fission at these excitation wavelengths are observed to carry very much higher levels of vibrational excitation in the above two modes. The observation of H atoms attributable to secondary photolysis of SH(X) fragments indicates increased competition from the alternative C–S bond fission channel at these shorter excitation wavelengths. Additional peaks in the H atom time-of-flight spectrum, most clearly evident following excitation at wavelengths in the range 213–220 nm, are interpretable in terms of secondary photolysis of the primary CH3S(X) fragments yielding... [ABSTRACT FROM AUTHOR]