Developing novel luminescent materials with ideal properties is an endless project, urged by growing requirements of advances in energy saving, healthy lighting and environmental friendliness. Herein, a series of ScCaOBO3:Ce3+,Mn2+ phosphors with excellent luminescence properties were synthesized by the high temperature solid state method. X-ray diffraction was applied to analyse the phase composition of the obtained phosphors. The morphology and dopant distribution were observed by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS), respectively. The Rietveld refinements and luminescence spectra indicate that Ce3+ preferentially occupies the Sc3+ site and produces a blue emission band at around 460 nm, which originates from the characteristic 5d-4f transitions, while Mn2+ preferentially occupies the Ca2+ site and emits red light due to its characteristic 4T1(4G)-6A1(6S) transitions. Upon excitation at 354 nm, both Ce3+ and Mn2+ emissions can be obtained and further investigations evidenced that the broad and intense light emission of Mn2+ located in the red spectral region is the result of energy transfer from Ce3+ to Mn2+. Theoretical calculations reveal that the energy transfer process from Ce3+ to Mn2+ is of the resonance type and is governed by electric dipole-dipole interactions. Since the ScCaOBO3:Ce3+,Mn2+ phosphors are capable of producing broadband emissions that widely cover the blue and red spectral regions, the introduction of a green light-emitting phosphor CMA:Tb3+ can conveniently generate high quality white light. Therefore, a white light-emitting diode device with extremely high color rendering indices, Ra = 93.7 and R9 = 91.9, was successfully obtained.