We report the first results of molecular frame photoelectron emission for dissociative photoionization (DPI) of H 2 and D 2 molecules induced by a spectrally filtered single high harmonic of a few femtosecond duration, using coincident electron–ion velocity vector correlation techniques. For the studied photon energies around 32 eV, where the resonant excitation of the Q 1 and Q 2 doubly excited states occurs, autoionization and nuclear dynamics are coupled on a few femtosecond timescale, giving rise to quantum interferences. Molecular frame photoelectron angular distributions (MFPADs), traced as a function of the kinetic energy release of the atomic fragments, provide the most sensitive observables for such complex dynamics. These results compare well with recent spectrally resolved experiments using synchrotron radiation which are also reported. As a novel XUV light source running at multi-kHz repetition rate and synchronized with laser pulses, high-order harmonic generation (HHG) opens new possibilities for extending these investigations to time-resolved studies at the femtosecond scale.