The inspiration of the present work emerges from the formulation to enhance the combustion, emission and performance of a single cylinder diesel engine through modifying the fuel by adding an additive together with water-in-diesel emulsion fuel. 1,4-dioxane a hygroscopic, multipurpose substance was considered as one of the irreplaceable additive to be included with the ideal mix of DWS (89.8%diesel + 10%water + 0.2%surfactant) to enhance the engine attributes. In the present work, 1,4-dioxane was mixed with the optimized blend of DWS (10% water and 89.8% diesel), with varying concentrations of 5, 10, 15, 20% and denoted as DWSA5, DWSA10, DWSA15, DWSA20 respectively. With the expansion of 1,4-dioxane, the physical properties were enhanced. The sample fuels were analyzed with Fourier-transform infrared spectroscopy (FTIR) in order to find functional groups. An experiment was conducted with test fuels in a single cylinder, unmodified diesel engine. From the experimental data, it was revealed that, brake thermal efficiency (BTE) of DWSA10 increases up to 7% when compared with diesel fuel. Hydrocarbon (HC) and smoke decreases up to 31.66%, 27.83% respectively with diesel fuel. Brake specific energy consumption (BSEC) and carbon monoxide (CO) of DWSA10 decreased about 7.5%, 15% respectively on par with DWS fuel. From the obtained results, it was identified that test fuel (DWSA10) containing 10% 1,4-dioxane shows significant improvement in the engine performance and reduction in emission. DWSA10 may play a significant role for diesel engine in future without modifying the engine.