Herein, we report the synthesis and characterization of two Pt(II) coordination compounds, the new platinum(II)[N,N′-bis(salicylidene)-3,4-diaminobenzophenone)] ([Pt(sal-3,4-ben)]) and the already well-known platinum(II)[N,N′-bis(salicylidene)-o-phenylenediamine] ([Pt(salophen)]), along with their application as guests in a poly [9,9-dioctylfluorenyl-2,7-diyl] (PFO) conjugated polymer in all-solution processed single-layer white organic light-emitting diodes. Completely different performances were achieved: 2.2% and 15.3% of external quantum efficiencies; 2.8 cd A−1 and 12.1 cd A−1 of current efficiencies; and 3103 cd m−2 and 6224 cd m−2 of luminance for the [Pt(salophen)] and [Pt(sal-3,4-ben)] complexes, respectively. The Commission Internationale de l’Eclairage (CIE 1931) chromaticity color coordinates are (0.33, 0.33) for both 0.1% mol/mol Pt(II):PFO composites at between approximately 3.2 and 8 V. The optoelectronic properties of doped and neat PFO films have been investigated, using steady-state and time-resolved photoluminescence. Theoretical calculations at the level of relativistic density functional theory explained these results, based on the presence of the Pt(II) central ion’s phosphorescence emission, considering spin-orbit coupling relationships. The overall results are explained, taking into account the active layer morphological properties, along with the device’s electric balance and the emitter’s efficiencies, according to deep-trap space-charge models. Considering the very simple structure of the device and the ease of synthesis of such compounds, the developed framework can offer a good trade-off for solution-deposited white organic light-emitting diodes (WOLEDs), with further applications in the field of lighting and signage.