Efficient Ca₁₄Zn₆Al₁₀O₃₅: Mn⁴⁺, Nd³⁺/Yb³⁺ spectral conversion materials have been prepared by a sol–gel method. The Ca₁₄Zn₆Al₁₀O₃₅: Mn⁴⁺, Nd³⁺/Yb³⁺ materials can efficiently shift the short-wavelength sunlight in 250–550 nm spectral regions into near infrared emission which matches the higher sensitivity region of Si-based solar cells. The maximal energy transfer efficiency is 76.0% and 80.4% in Mn⁴⁺, Nd³⁺ and Mn⁴⁺, Yb³⁺ co-doped samples when excited at 460 nm, respectively. A dipole–dipole interaction is responsible for the energy transfer sensitization processes from Mn⁴⁺ to Nd³⁺/Yb³⁺ ions, which has been confirmed by Dexter's theory and the Yokota–Tanimoto model.