Research on chiral selection and recognition not only is of fundamental importance in resolving the origin of biological homochirality, but also is instructive in the fabrication of controlled molecular organization in supramolecular systems to modulate their chirality-related functional properties. Here we report an enantioselective assembly process between a chiral energy donor and two enantiomeric energy acceptors, which further results in chirality-controlled energy transfer and enantioselective triplet-triplet annihilation upconversion (TTA-UC). It is found that the chiral energy donor Pd(II) octaethylporphyrin derivative PdOEP-LG12 (RD) can selectively coassemble with the chiral energy acceptor LGAn (RA) with the same chiral scaffold but tends to form segregation with the energy acceptor DGAn (SA) with the opposite chiral scaffold in a thermodynamic equilibrium state. Thus, the coassembly of RA/RD shows more effective triplet-triplet energy transfer (TTET) and stronger upconverted luminescence and upconverted circularly polarized luminescence in comparison to the segregation of SA/RD. The establishment of such an enantioselective TTA-UC system highlights the applications of chirality-regulated triplet fusion in optoelectronic materials.