Excitation of the 4f(3) ion Nd3+ in hexafluoroelpasolite lattices by synchrotron radiation of wavelength similar to 185 nm leads to fast 4f25d -> 4f(3) emission below 52 630 cm(-1) and slower 4(f)3 -> 4f(3) emission from the luminescent states F-4(3/2) Gamma(8u) (11 524 cm(-1)) and (2)G(2)(9/2) Gamma(8u) (similar to 47 500 cm(-1)). The near-infrared emission is well-resolved, and a clear interpretation of the I-4(9/2) crystal field levels and of the one-phonon vibronic sideband is given. The excitation spectrum of the (2)G(2)(9/2) emission enables clarification of the structure of the 4f25d configuration (which extends from similar to 52 000 to 128 000 cm(-1)). Detailed energy level and intensity calculations have been performed, which provide simulations of the d-f emission and the f-d excitation spectra in good agreement with experiment. It is interesting that although the 4f(3) (2)G(2)(9/2) Gamma(8u) -> 4f(3) I-4(J) transitions are very weak in intensity compared with transitions terminating upon higher multiplet terms, most of the 4f(2)5d (H-3) I-4(9/2) Gamma(8g) -> 4f(3) emission intensity resides in the transitions to I-4(J).