The fluorescence behaviour of substituted dialkyl-aminobenzoic esters was investigated in different thermotropic 4-cyano-bicyclohexyl-4’-alkyl compounds. It was found that these materials show more than one charge-transfer emission. This behaviour is unusual and it is dependent on the nature of the probe, the nature of the mesophase and the structure of the liquid-crystalline compound itself. Guest-host and host-host interactions are discussed for a complete understanding of the probe behaviour. Both stationary and time-resolved fluorescence measurements indicate that guest-guest interactions dominate more in the smectic phase than in the nematic phase. Furthermore, the formation of the charge transfer occurs faster in the nematic phase than in the smectic phase.