Organic small molecules exhibiting both thermally activated delayed fluorescence (TADF) and wide-ranging piezochromism (Δλ > 150 nm) in the near-infrared region have rarely been reported in the literature. We present three emitters MeTPA-BQ, tBuTPA-BQ and TPPA-BQ based on a hybrid acceptor, benzo[g]quinoxaline-5,10-dione, that emit via TADF, having photoluminescence quantum yields, Φ_PL, of 39–42% at photoluminescence (PL) maxima, λ_PL, of 625–670 nm in 2 wt% doped films in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP). Despite their similar chemical structures, the PL properties in the crystalline states of MeTPA-BQ (λ_em = 735 nm, Φ_PL = 2%) and tBuTPA-BQ (λ_em = 657 nm, Φ_PL = 11%) are significantly different. Further, compounds tBuTPA-BQ and TPPA-BQ showed a significant PL shift of ∼98 and ∼165 nm upon grinding of the crystalline samples, respectively. Deep-red organic light-emitting diodes with MeTPA-BQ and tBuTPA-BQ were also fabricated, which showed maximum external quantum efficiencies, EQE_max, of 10.1% (λ_EL = 650 nm) and 8.5% (λ_EL = 670 nm), respectively.