Three compounds 4-naphthyltriphenylamine(a), methyl 13-［N,N-(4-naphthylphenyl)- phenyl］aminodeisopropyldehydroabietate(b) and methyl 13-［N,N-Bis(4-naphthylphenyl)］aminodeisopropyldehydroabietate(c) were synthesized by esterification, bromine reaction, nitration reaction, reduction reaction and C-N coupling reaction using triphenylamine and dehydroabietic acid respectively. Their structures were characterized by 1H MNR, 13C MNR, and MS. In order to study the relationship between structures and spectral properties of compounds, molecular configuration of compounds were optimized by DFT/B3LYP using Gaussian 09, then their bond lengths, bond angles, and dihedral angles were obtained and compared. The results show that the introduction of dehydroabietic acid skeletons and naphthalene rings affect the coplanarity and the introduction of naphthalene rings increase their conjugated degree. Their fluorescence emission spectra and UV absorption spectra in five solvents with decreasing polarity, such as methanol, dioxane, THF, dichloromethane and cyclohexane were also studied. The results show that the maximum fluorescence emission wavelengths of compounds differ greatly in different polar solvents. The fluorescence emission wavelength is the largest in methanol, and which is the smallest in cyclohexane, however, the fluorescence emission wavelengths are not increase with increasing polarity, the fluorescence emission wavelengths of compounds have large degree of blue-shift in dichloromethane, THF and dioxane with increasing polarity. In the same solvent, the maximum fluorescence emission wavelengths of compounds b and c were red-shift relative to compound a, the red-shift degree of compound c was similar to that of compound b. In UV absorption spectra, the maximum absorption wavelengths of compounds a, b and c in different polar solvents are also different. In 200～250 nm range, their maximum absorption wavelengths have big shift in dichloromethane from which is in other four solvents, but in 300～350 nm range, their maximum absorption wavelengths have big shift in methanol, and they have almost the same wavelengths in five solvents in 250～300 nm range. In the same solvent, their maximum absorption wavelengths in 300～350 nm range differ greatly, and compound c has a big red-shift (26 nm) from a. Combining with the structural optimization datas, it shows that the conjugated degree of compounds has a great effect on the fluorescence emission spectra and the UV absorption spectra, however, coplanarity affects the fluorescence emission spectra of compounds significantly. The differences in fluorescence emission spectra and UV absorption spectra of compounds a, b and c in different polar solvents indicate that three compounds have significant solvatochromism effect, which means they have potential to be used as fluorescent probes in different polar environment.