We present femtosecond time-resolved photoelectron spectra and ab initio studies on pyrazole andits methylated derivatives 1-, 3-, and 5-methylpyrazole. Excitation at 200 nm populates both the two lowest lying states, a 1ππ* state and a mixed 1πσ*/1π3s Rydberg state, from where three relaxation channels are observed: ring puckering, N-H bond cleavage, and ring opening via N-N bond breaking. The N-N bond breaking channel is the fastest process, occurring within one vibrational cycle of the Franc Condon active ring stretching mode. N-H bond cleavage is observed to be aminor channel, and occurs upon direct excitation to the mixed π3s/πσ* state. Finally, ring puckering occurs after a timescale of a few hundred fs because the molecules need time to find the gradient towards this conical intersection. However, this channel is accessed if the initially triggered processes are not successful. The quantum yields of the different channels were found to be very sensitive of the relative positioning of the excited states. In pyrazole and 5-methylpyrazole, N-Nbond cleavage dominates. In 1-, and 3-methylpyrazole, while the 1ππ* state drops in energy the dissociating 1πσ* valence state does not, and this leads to an increased barrier towards ring cleavage and a decreased the quantum yield for N-N bond cleavage. Upon excitation at 267 nm of 1- and 3-methylpyrazole, ring puckering is the only available pathway.