A novel rotational spectroscopy method applicable to ions stored in cold traps is presented. In a double resonance scheme, rotational excitation is followed by vibrational excitation into a dissociative resonance. Its general applicability is demonstrated for the CH_{3}^{+}-He complex, which undergoes predissociation through its C-H stretching modes ν_{1} and ν_{3}. High resolution rotational transitions are recorded for this symmetric top, and small unexpected splittings are resolved for K=1. Advantages and potential future applications of this new approach are discussed.