The cyclometalated Pt(ii) acetylide derivative with a 1,3-bis(N-octyl-benzimidazol-2-yl)benzene (N^C^N) ligand and a free terpyridine (TPY) receptor has been successfully synthesized and characterized. X-ray crystallography shows its inefficient conjugation degree between the [(N^C^N)Pt] and TPY planes. This bifunctional complex shows an enhanced 1MLCT/LLCT absorption band (ε = 3.30 × 104 dm3 mol-1 cm-1) centered at λmax = 365 nm, and the well-resolved vibronic-structured 3MLCT/LLCT emission bands (Φ = 0.08, τ = 3.43 μs) in the range of ca. 475-700 nm. Consecutive titrations show that added Zn2+ and Eu(HFA)3 bond to its free TPY receptor with 1 : 2 and 1 : 1 stoichiometry to form the heterotrinuclear Pt-Zn-Pt (Ka = 3.48 × 104 mol-1 dm3) and heterodinuclear Pt-Eu (Ka = 1.73 × 104 mol-1 dm3) complexes, respectively. A sensitizing effect of Zn2+ on the TPY unit, and the incomplete d → f energy transfer from the [(N^C^N)Pt(ii)] antenna donor to the Eu(iii) center with maximum efficiency of 51.8% are observed. Using an in situ mixed titration strategy, the R/G/B emission triads consisted of red [(TPY)Eu(HFA)3] and green [(N^C^N)Pt(ii)] dual phosphorescence and blue [(TPY)Zn(TPY)] fluorescence, which can be well balanced to realize the white-light-emission with CIE coordinates (x = 0.36, y = 0.36) by precisely controlling the molar ratio (9 : 1 : 2) of the parent complexes, Eu(HFA)3 and Zn(ClO4)2.