4-Hydroxycoumarins are compounds with a lot of applications as drugs and herbicides. They have very interesting spectral and chemical properties, which are investigated theoretically and experimentally. Some new 4-hydroxycoumarins with arylydene--ketoester or arylydene-2,4-pentanedione side chain were synthesized by two step synthetic scheme. Their structure was characterized by UV-vis, IR, and 1 H NMR methods. The spectral behavior of the optimized structures of these compounds was reproduced by the hybrid DFT methods B3LYP and B3P86 with 6-31G** and augcc-pVDZ basis sets. Electronic excited states and vibrational frequencies were calculated. HF method was also used for comparison, because of the lack of electronic correlation. The theoretical spectra were compared with the experimental ones. A lot of compounds show good agreement between experimental and some of the theoretical data, especially obtained by aug-cc-pVDZ basis set.