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A set of new triple molybdates, Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45, was successfully manufactured by the microwave-accompanied sol–gel-based process (MAS). Yellow molybdate phosphors Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 with variation of the Li_xNa_1-x (x = 0, 0.05, 0.1, 0.2, 0.3) ratio under constant doping amounts of Ho³⁺ = 0.05 and Yb³⁺ = 0.45 were obtained, and the effect of Li⁺ on their spectroscopic features was investigated. The crystal structures of Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) at room temperature were determined in space group <i>I</i>4₁/<i>a</i> by Rietveld analysis. Pure NaCaGd_0.5Ho_0.05Yb_0.45(MoO₄)₃ has a scheelite-type structure with cell parameters <i>a</i> = 5.2077 (2) and <i>c</i> = 11.3657 (5) Å, <i>V</i> = 308.24 (3) ų, <i>Z</i> = 4. In Li-doped samples, big cation sites are occupied by a mixture of (Li,Na,Gd,Ho,Yb) ions, and this provides a linear cell volume decrease with increasing Li doping level. The evaluated upconversion (UC) behavior and Raman spectroscopic results of the phosphors are discussed in detail. Under excitation at 980 nm, the phosphors provide yellow color emission based on the ⁵S₂/⁵F₄ → ⁵I₈ green emission and the ⁵F₅ → ⁵I₈ red emission. The incorporated Li⁺ ions gave rise to local symmetry distortion (LSD) around the cations in the substituted crystalline structure by the Ho³⁺ and Yb³⁺ ions, and they further affected the UC transition probabilities in triple molybdates Li_xNa_1-xCaGd_0.5(MoO₄)₃:Ho³⁺_0.05/Yb³⁺_0.45. The complex UC intensity dependence on the Li content is explained by the specificity of unit cell distortion in a disordered large ion system within the scheelite crystal structure. The Raman spectra of Li_xNa_1-xCaGd_0.5(MoO₄)₃ doped with Ho³⁺ and Yb³⁺ ions were totally superimposed with the luminescence signal of Ho³⁺ ions in the range of Mo–O stretching vibrations, and increasing the Li⁺ content resulted in a change in the Ho³⁺ multiplet intensity. The individual chromaticity points (ICP) for the LiNaCaGd(MoO₄)₃:Ho³⁺,Yb³⁺ phosphors correspond to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates.