The weakly bound Al-CH4 complex, and the fully deuterated version, Al-CD4, were prepared in a pulsed supersonic beam and probed with laser fluorescence excitation spectroscopy. Transitions to bound vibrational levels in electronic states correlating with the Al(5s,4d) + CH4/CD4 dissociation asymptotes have been observed. Resonance fluorescence from the excited levels could not be detected. Rather, these excited levels decay nonradiatively, and the excitation spectrum was obtained by monitoring emission from the lower Al atomic levels and AIH A - X chemiluminescence from formation of AIH(A(1)Pi) within the excited complex. The band systems were dominated by progressions in the excited-state Al-CH4/CD4 van der Waals stretch vibrational mode. It was not possible to make unambiguous upper-state vibrational quantum number assignments, and lower bounds to excited-state binding energies were obtained. Band contour analysis of the AlH chemiluminescence spectra indicates that the excited AIH(A(1)Pi) product is formed with approximately equal h-doublet populations, in contrast to the marked propensity for formation of e levels in the reactive decay of the Al(5s)-H-2 complex [Yang, X.; Dagdigian, P. J. J. Chern. Phys. 1998, 109, 8920].