AbstractSix conjugated platinum(II) acetylides with multibranched donor‐acceptor structures (1–6) were synthesized. The absorption maxima of triazine‐centered complexes 1–3 are red‐shifted by 36–43 nm compared with those of triphenylamine‐centered complexes 4–6. The luminescence spectra of 4–6 in air‐saturated chloroform showed one fluorescence peak and one phosphorescence peak. However, only one fluorescence peak was detected for 1–3 in air‐saturated chloroform. The transient absorption spectra of the compounds indicate the effective intersystem crossing from S1 to T1. The nonlinear optical properties of 1–6 in N,N‐dimethylformamide were studied using open Z‐scan method. The results indicate that complexes 1 and 6 exhibit good nonlinear optical performance. The ratios of the effective nonlinear absorption cross section to ground‐state absorption cross section σeff/σ0 of complexes 1–6 are in the range of 4–22.