Treatment of a number of 4-substituted arylazobenzenes (-H, -Me, -CF3, -Br, -F and -OMe) with Et2O.BF3 in dry chloroform solution afforded chromophores that exhibited significant hyper- (log 3 4.41-4.60) and bathochromic shifts (lambdamax 416-473) in electronic spectra, together with significant shifts in their 1H NMR and 13C NMR spectra, indicating the formation of novel chemical species. It is proposed that complexes are formed between the azo dyes and the Lewis acid, similarly to what happens for the well-known protic acids. The equilibrium constants (log K ) of the proposed complexes have been calculated from the experimental data. Numerical modelling has also been performed to investigate the nature of the new systems, revealing a correlation between the electronic levels of the azo dye and the ones of the BF3.OEt2.