Herein, we describe the synthesis of tunable aryl imidazolium ionic liquid catalysts and tested for esterification of fatty acids to biodiesel. In this work, six tunable aryl imidazolium ionic liquids (TAIILs) 1a-1f were prepared. These ionic liquids were used as the economical and reusable catalysts for the synthesis of biodiesel fuels. The reaction has been preceded in a monophase at 80 degrees C for 4 h, after which the product was separated from the catalyst system by a simple liquid/liquid phase separation at room temperature with excellent yields. With the simple post-process, the catalyst is reusable at least 6 times. This novel method offers a short reaction time, good yields, and environmentally benign characteristics.