We employ classical porphyrins, as well as second-generation sensitizers, such as tetrabenzo- porphyrins, naphthaloporphyrins, texaphyrins, and sapphyrins for biological photosensitization. We studied the extent of sensitizer binding to biological membranes and bacterial cells; the singlet oxygen production yield in homogeneous solutions and in membranes; and the efficiency of the photo-cytotoxic effect of the sensitizers. In carrying out these studies, absorption and fluorescence spectra were used as monitoring techniques. We demonstrate a spectroscopic probing procedure, based on the well established chemical quencher of singlet oxygen, DPIBF, which at appropriate concentration allows a simple mathematical evaluation of the absolute quantum yield of singlet oxygen production. The method does not rely on any predetermined kinetic values and provides a result with high accuracy. The relative efficiency of competing photochemical processes in cells was established, so that the likely mechanism which is responsible for the death of the cell could be pointed out. A unique and exceptional wavelength dependence of photophysical properties is described.