Chemical Engineering processes demands separation of reaction products to obtain them in purest form. Reactive Distillation facilitates this feature by incorporating a reactive zone for reaction between conventional rectifying and stripping zone for distillation. It also aid for solid catalyst incorporation of amphoteric nature to avoid repetitive addition of catalyst for different experimental run and will also improve the product yield. The other beneficial features of Reactive Distillation include reduced synthesis cost, reduced utility space required and higher selectivity. This technique is introduced in this paper for synthesis of oxygenated bio-fuel. For this, fuel additive of ether family namely Tert Amyl Ethyl Ether (TAEE) is synthesized using ethanol. Similarly, Biodiesel synthesis is done using transesterification of waste cooking oil with methanol. Both fuel-oxygenate (TAEE) and biodiesel are then blended in varying proportion to improve ignition quality of biodiesel fuel. The study is done experimentally and analyzed under object oriented modeling mode in simulation. Optimization of synthesis process is done using revamping in experimental mode corresponding to sensitivity analysis in simulation. The congruence results show that purity of 95 % and 65 % for biodiesel and TAEE respectively is obtained in reactive distillation corresponding to reboiler duty of 2 kW and reflux ratio 4.