The phototransformation of protochlorophyllide forms was studied in epicotyls of dark-germinated pea (Pisum sativum L. cv. Zsuzsi) seedlings. Middle segments were illuminated with white or 632.8 nm laser flash or continuous light at room temperature and at À15 C. At low light intensities, photoreduction could be distinguished from bleaching. 77 K fluorescence emission spectra were measured, difference spectra of illuminated and nonilluminated samples were calculated and/or the spectra were deconvoluted into Gaussian components. The 629 nm-emitting protochlorophyllide form, P629 (Pxxx where xxx is the fluorescence emission maximum), was inactive. For short-period (2-100 ms) and/or low-intensity (0.75-1.5 mmol m À2 s À1 ) illumination, particularly with laser light, the transformation of P636 into the 678 nm-emitting chlorophyllide form, C678 (Cxxx where xxx is the fluorescence emission maximum), was characteristic. This process was also found when the samples were cooled to À15 C. The transformation of P644 into C684 usually proceeded in parallel with the process above as a result of the strong overlap of the excitation bands of P636 and P644. The Shibata shift of C684 into a short-wavelength form, C675-676, was observed. Long-period (20-600 s) and/or high-intensity (above 10 mmol m À2 s À1 ) illumination resulted in the parallel transformation of P655 into C692. These results demonstrate that three flash-photoactive protochlorophyllide forms function in pea epicotyls. As a part of P636 is flash photoactive, its protochlorophyllide molecule must be bound to the active site of a monomer protein unit [Bö ddi B, Kis-Petik K, Kaposi AD, Fidy J, Sundqvist C (1998) The two short wavelength protochlorophyllide forms in pea epicotyls are both monomeric. Biochim Biophys Acta 1365: 531-540] of the NADPH:protochlorophyllide oxidoreductase (EC 1.3.1.33). Dynamic interconversions of the protochlorophyllide forms into each other, and their regeneration, were also found, which are summarized in a scheme.Abbreviations -Chl, chlorophyll; Chlide, chlorophyllide; Cxxx, chlorophyllide form with fluorescence emission maximum at xxx nm; Pchl, protochlorophyllide ester, i.e. 'protochlorophyll'; Pchlide, protochlorophyllide; Pxxx, protochlorophyllide or protochlorophyll form with fluorescence emission maximum at xxx nm; PLB, prolamellar body; POR, NADPH: protochlorophyllide oxidoreductase enzyme (POR, EC 1.3.1.33); PT, prothylakoid.