N-(substituted-benzoyl)-1-aminonaphthalenes and N-(substituted-benzoyl)-2-aminonaphthalenes (1-NBAs and 2-NBAs) with varied substituents at the para- or meta-position of benzoyl phenyl ring were prepared to probe the difference between 1-aminonaphthalene (1-AN) and 2-aminonaphthalene (2-AN) as electron donors, using benzanilide-like charge transfer as a probe reaction. An abnormal long-wavelength emission was found for all of the prepared aminonaphthalene derivatives in cyclohexane and was assigned to the CT state by the observation of a substantial red shift with increasing solvent polarity or with increasing electron-withdrawing ability of the substituent. The CT emission energies were found to follow a linear relationship with the Hammett constant of the substituent and the value of the linear slope for 1-NBAs (−0.45 eV) was higher than that of 2-NBAs (−0.35 eV), the latter being close to that of the aniline derivatives (BAs, −0.345 eV). This pointed to a higher extent of charge separation in the CT state of 1-NBAs in which a full charge separation was established by the reduction potential dependence of the CT emission energy with a linear slope of −1.00. The possible contribution of the difference in the steric effect and the electron donating ability of the donors in 1-NBAs and 2-NBAs was ruled out by the observation that the corresponding linear slopes of benzoyl-substituted BAs remained unchanged when para-, meta-, ortho-, or ortho,ortho-methyls were introduced into the aniline moiety. It was therefore concluded that 1-AN enhanced the charge transfer in 1-NBAs and the proximity of its ¹L_a and ¹L_b states was suggested to be responsible. Results showed that the charge transfers in 1-NBAs and 2-NBAs were not the same and 1-AN and 2-AN as electron donors were different not only in electron donating ability but in shaping the charge transfer pathway as well.