The present work aims at to improve the engine performance and emission reduction from diesel engine by the addition of fuel additive 1,4-dioxane to the optimum blend (A20) for Annona biodiesel through alternate the fuel properties. The additive (1,4-dioxane) is mixed with optimum blend (A20) in different proportions ranging from 5ml to 10ml such as A20-5ml and A20-10ml (99.0% of A20+1.0% of 1,4-Dioxane). The addition of additive 1,4-dioxane with Annona biodiesel improve the properties of cold flow and ignition temperature. From the results, it was observed that the brake thermal efficiency for A20-10ml is improved by 6.48% when compared to that of A20 without additive at full condition. Further the hydrocarbon (HC), carbon monoxide (CO), oxides of nitrogen (NOx) and smoke for A20-10ml is reduced by 29.7%, 20%, 16.87% and 25.51% respectively when compared to that of A20 at full load condition. Hence the A20-10ml blend is the appropriate blend to improve the performance is better and reduced exhaust emissions from diesel engine without any engine modification.