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The fragmentation dynamics of pyrrole molecules following excitation at many wavelengths in the range 193.3 < λphot < 254.0 nm have been investigated by H Rydberg atom photofragment translational spectroscopy. Excitation at the longer wavelengths within this range results in (vibronically induced) population of the 11A2(πσ*) excited state, but once λphot ≤ 225 nm the electric dipole allowed 11B2 ← X1A1(π* ← π) transition becomes the dominant absorption. All of the total kinetic energy release (TKER) spectra so derived show a ‘fast’ peak, centred at TKER ∼7000 cm−1. Analysis of the structure evident in this peak, particularly in spectra recorded at the longer excitation wavelengths, reveals selective population of specific vibrational levels of the pyrrolyl co-fragment. These have been assigned by comparison with calculated normal mode vibrational frequencies, leading to a precise determination of …