We developed sensing platforms to detect and differentiate various types of biogenic amines, cadaverine, putrescine, spermine, histamine, tyramine and tryptamine by monitoring the changes in fluorescence signal. The sensing platforms comprised a carboxylated polyfluorene derivative doped with benzothiadiazole acceptor moieties in a small fraction (20%). When utilized as an individual sensing component, the conjugated polyelectrolyte detects all BAs nonselectively via binding-induced fluorescence quenching. If the conjugated polyelectrolyte forms an intermediary charge-driven complex with an oppositely charged surfactant, a Förster resonance energy transfer (FRET) response is triggered. Biogenic amines are detected through their effects on the FRET signal as enhancement, reduction, or no effect. We formed intermediary charge-driven complexes at nonstoichiometric, cation deficient and excess conditions. Supramolecular interactions governed the co-assembly and disassembly caused by the targeted amines on the conjugated polyelectrolyte-surfactant complex. Therefore, structural and charge-related differences enabled their selective detection in our sensing platforms. Among them, spermine exhibited the highest FRET enhancement effect due to its polycationic aliphatic structure by engaging in multi-point interchain contacts among conjugated polyelectrolyte chains. In contrast, tryptamine showed a unique quenching effect on the FRET signal due to the steric hindrance created by its bulky, heterocyclic structure, leading to the dissociation of the complexes.