Thermally activated delayed fluorescence (TADF)-based electroluminescence (EL) devices adopting a host/guest strategy in their emitting layer (EML) are capable of realizing high efficiency. However, TADF emitters composed of donor and acceptor moieties as guests dispersed in organic host materials containing a donor and/or an acceptor are subject to donor-acceptor (D-A) interactions. In addition, electron delocalization between neighboring emitter molecules could form different species of aggregates. Here, we investigate the effects of intermolecular interacting emission species on the optoelectronic properties of sky-blue/green/red (sB/G/R) TADF emitters as guests using poly(biphenyl-Si/Ge) grafted with various donor moieties as hosts. We found the presence of guest/guest exciplex (Dg/Ag)*, host/guest exciplexes (Dh/Ag)*, and aggregates through the exploration of interactions between neighboring TADF guest molecules and between host and TADF-guest molecules. The nonradiative 3(Dh/Ag)* (ΔEST ≈ 0.5 eV) could increase the internal conversion rate (kIC) and reduce delayed luminescence, and both of them could cause a decrease in PLQY. The luminescence of 3(Dh/Ag)* may have a positive or negative effect on PLQY depending on its triplet energy. As the singlet and triplet energies of (aggregate)* are lower than those of (ICT)*, energy transfer from (ICT)* to (aggregate)* could occur. The low PLQY nature of (aggregate)* means that it is more likely to cause quenching in device emission. The emissions from (Dh/Ag)* and (aggregate)* are found to have increased full width at half-maximum and lead to lower emission color purity. Such intermolecular interactions should also occur in host/guest (TADF) systems and nondoped TADF emitter systems and thus are important factors for the molecular design of the TADF emitter and/or its accompanying host for high device efficiency and emission color purity.