The isolated subcomplex LHCI-730 of plant photosystem I (PSI) chlorophyll (Chl) alb binding antenna is a heterodimer of Lhca1 and Lhca4 and has a 77 K fluorescence emission peak at 730 nm (F730). Recently, three Chl spectral forms with 77 K fluorescence emission peaks at 720 nm, 730 nm and 742 nm were identified in native PSI. In an attempt to assign the two longest wavelength emission maxima to peripheral PSI antenna proteins, we performed 77 K fluorescence emission spectroscopy on intact leaves of chlorina and viridis mutants from barley which lack individual LHCI-730 proteins. This approach indicates that F732 is found only in Lhca1 and F742 only in Lhca4, when these proteins are associated with the PSI reaction centre.