Multidimensional spectroscopies have shaped our understanding of molecular phenomena, but they are often limited in sensitivity. In this work, we describe two-dimensional bond-selective fluorescence-detected infrared-excited (2D-BonFIRE) spectro-microscopy: an ultrasensitive two-dimensional spectroscopy and hyperspectral imaging technique. 2D-BonFIRE spectra are richly detailed, allowing for direct measurement of vibronic coupling and strong evidence of combination modes in congested spectral regions. Additionally, 2D-BonFIRE provides new insights into the nature of vibrational relaxation, including direct experimental observation of vibrational cooling rate dispersion, illuminating the inherent heterogeneity of vibrational decays in large molecules. Finally, we demonstrate that the high specificity of 2D-BonFIRE allows for single-shot 16-colour chemical imaging, with high promise for further palette expansion. 2D-BonFIRE holds significant potential as a tool for fundamental photophysics and a basis for super-multiplex bioimaging.