The dynamic nonlinear absorption of a chloroform solution of chlorophyll A was investigated using the Z-scan technique with picosecond pulses at 532 nm. The nonlinear absorption exhibits a reverse saturation, indicating a strong intersystem crossing (singlet–triplet) process. The time evolution of the optical nonlinearity, modeled by means of a five-level energy diagram, allows the determination of excited-state cross sections and the lifetime of the intersystem crossing based on its absorption characteristics and efficient formation of triplet states. Chlorophyll A was found to be a good candidate for a sensitizer in photodynamic therapy.