State of the art DFT calculations indicate that 3-(phenylamino)-2-cyclohexen-1-one (PACO), a β-enaminone, is capable of forming 1:1 microclusters with a variety of oxygen donor solvents in the ground state through its hydrogen bond donor unit (N–H). The computed N–H bond lengths and N–H stretching frequencies correlate fairly well with the H-bond donating and accepting abilities of the solvents together with their polarities through Kamlet–Taft type of equations. Experimental IR spectra in bulk solvents indicate that there could be additional microsolvation also through the H-bond accepting unit of the probe. Our calculations indicate that PACO forms 1:3 microclusters with water through simultaneous solvation at the C=O and the N–H moieties. The computed IR spectrum of this 1:3 microcluster suggests that H-bonding at the H-bond donor site can be cooperatively affected by H-bond formation at the Hbond accepting site of PACO.