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This study examines the impact of the addition of bio-ethanol/bio-ETBE on the main volatility properties of gasoline. Although several studies have been published on the addition of ethanol or ETBE to gasoline, the simultaneous addition of these oxygenates has not been studied by taking the maximum oxygen content of 3.7% m/m into account. The EN 228:2012-A1:2017 standard specifies the requirements for marketed unleaded gasoline. This standard is able to determine, among other things, a gasoline type with a maximum oxygen content of 3.7% m/m and sets the maximum limits for ethanol content at 10% v/v and 22% v/v for ethers with a minimum five carbon atoms, such as ΕΤΒΕ. Five refinery fractions were mixed in various proportions and were used as base fuels. A total of 30 samples were prepared by blending the base fuels with bio-ethanol/bio-ETBE. In each of these base fuels, bio-ethanol was added in concentrations up to 10% v/v. Subsequently, bio-ETBE was added to each of these fuels in concentrations up to 20.8% v/v for use as a stabilizer. All of the samples were examined using the EN ISO 13016-1 and EN ISO 3405 test methods while considering the volatility requirements set by EN 228. The results showed that the addition of bio-ETBE has a beneficial effect on the volatility characteristics of the samples, as it reduces the vapor pressure of the final blend and sets all fuels in compliance with the required specification limits set by the EN 228 standard.