We report the synthesis and characterization of two new mesoferrocenylporphyrins, with the ferrocenyl unit attached at the para position of a C 6 F 4 group by a C-N bond with -NH(CH 2 ) 2 NH-(2a) and -NH(CH 2 ) 4 NH-(2b) spacers. Compounds 2a and 2b were characterized through elemental analyses, electrospray ionization high-resolution mass spectrometry, 1 H NMR, UV-visible and fluorescence spectroscopies, electrochemistry and spectroelectrochemistry. The free base porphyrin 2 was included for comparison purposes. The binding ability of 2 and the porphyrin derivatives 2a and 2b with calf thymus DNA was determined using UV-visible and fluorescence spectroscopies. The results suggest that the interaction of these systems most probably occurs through π-stacking by non-classical modes involving the partial insertion of the C 6 F 5 ring between adjacent base pairs on DNA and possible hydrogen interaction with the aliphatic -NH(CH 2 ) n NH-(n = 2 or 4) groups with calf thymus DNA. Moreover, we also demonstrate that porphyrins generate singlet oxygen species and show good photostability after irradiation.