Herein, we have conducted a computational screen of 36 naphthalene-containing emitters to evaluate their promise as TADF emitters. Three of the compounds, 2-PXZ-Nap, 1-PXZ-Nap and 1,4-PXZ-Nap-PXZ, were then identified as being the most promising and were subsequently synthesised. The photophysical properties of these emitters in toluene solution and doped films in PMMA and mCP were measured. A high photoluminescence quantum yield of 48% and evidence of TADF were recorded for 1,4-PXZ-Nap-PXZ as a 20 wt% doped film in mCP. An OLED employing this emitter demonstrated an EQEmax = 10.5%, PEmax = 28.7 lm W -1 with green emission (λEL = 505 nm). This is, to the best of our knowledge, the first reported OLED utilising a TADF emitter in which naphthalene alone acts as the acceptor moiety. This initial study clearly demonstrates the potential of the acene acceptor design for the development of TADF emitters. Finally, a comprehensive computational study has been presented to demonstrate why naphthalene alone of the linear acenes is suitable for constructing donor-acene-donor TADF emitters of this type.