To explore the effect of substituent attached to aromatic ring and the length of diamine chain in salen-type Schiff base molecules on the fluorescence emission spectra (FL em ), the FL em of 63 diamine-salicylaldehyde condensates in an ethanol solution were obtained. The influence of substituent electronic effects and chain lengths on the wavenumber (ν em ) of fluorescence emission wavelengths (λ em ) was subsequently studied. The results show that the length of the diamine chain in the target compound has an effect on the ν em , which can be quantified by the alkyl polarizability effect index (PEI), where compounds with alkyl of higher PEI have lower ν em . Second, the λ em of salen-type Schiff bases can be quantified by an equation of the seven parameters, PEI, σ(X) ─OH , σ(X) ─CH═N , σ ex CC X ð Þ ─OH , σ ex CC X ð Þ ─CH═N , Δσ 2 p and Δσ 2 m , form where the stability and predictive ability of the obtained equation was confirmed by leave-one-out cross validation. Lastly, it was observed that the influence on the λ em of substituent X attached to the aromatic ring is related to its position relative to OH or CH═N groups as reference, whose Hammett constants (σ(X) ─OH , σ(X) ─CH═N ) and the excited-state substituent constants (σ ex CC X ð Þ ─OH , σ ex CC X ð Þ ─CH═N ) of the substituents X with varying locating methods have different effects on the λ em ;and that there is a "homoring competition effect" of substituent.