This work initiated a study on the preparation of assembled-spheres YVO₄:(Ln³⁺, Bi³⁺) (Ln = Eu, Sm, Dy, Ho), in which Bi³⁺ co-doping of a lower content, aims to achieve emission tailored for many applications by supressing the serious changes in host structures when higher concentrations of Bi³⁺ are involved. The formation of assembled-spheres is beneficial from the simultaneous dissolution of the starting Bi and Ln salts with the use of ethylene glycol. As a result, all assembled-spheres are featured by low surface absorbents and little interior lattice defects, which decreased the nonradiative rate to give a luminescence performance superior to other morphologies like cereal-like architectures. Further, four paths were applied to achieve the tunable multicolour-emission in these assembled-spheres, which include: (i) selecting the dopant Ln³⁺ with characteristic emissions; (ii) varying the concentration of dopant Ln³⁺; (iii) co-doping Ln³⁺/Bi³⁺ with dual emissions from Bi³⁺ and Ln³⁺; and (iv) adjusting the excitation wavelength. These tunable multicolour-emissions were demonstrated to be the consequence of the energy transfer process from the VO₄³⁻group to Ln³⁺ in YVO₄:Ln³⁺ or those from Bi³⁺ and the VO₄³⁻group to Ln³⁺ in the presence of lower Bi³⁺ content, as followed by a surprising red-shift of the absorption edge and extension of the luminescence lifetimes of Ln³⁺. The diverse approaches found in this work for emission tailoring are fundamentally important and may provide a general way to achieve multicolour-tunable emission for many applications.