Double-resonance spectroscopy, using collisional energy transfer to populate high-lying vibrational states, reveals the location of 27 previously undetected levels in the ground electronic state of HCN. Three laser-pumped overtones, (0,0degrees,4), (0,0degrees,5), and (1,0degrees,5) provide the doorway through which to collisionally populate vibrational levels lying between 10330 and 17650 cm(-1). This greatly increases the energy range over previous studies using collision-assisted spectroscopy and provides access to states which have internal energy above the predicted isomerization barrier. Levels populated by collisions from (0,0degrees,4) and (0,0degrees,5) are detected directly via A state fluorescence, while those from (1,0degrees,5) are detected through resonant multiphoton dissociation resulting in CN (B-->X) fluorescence. Although potentially, collision-assisted spectroscopy above the isomerization barrier could access HNC localized states, such states have not been identified in the present experiments.