Glow-discharge plasma was utilized for treating the KOH/carbonated calcium aluminate synthesized by MCM. Treated and untreated nanocatalysts were characterized by XRD, FESEM, EDX-dot mapping, TEM, TGA/DSC, FTIR and N-2 adsorption-desorption measurements. Moreover, some analyses were performed on the catalyst after assessment its catalytic activity in the microwave-assisted transesterification reaction. Treated and untreated nanocatalyst presented Ca12Al14O33 structure as support which was covered by carbon groups. The plasma treating was significantly effect on the potassium component as surface active phase and interaction of potassium and calcium with aluminium cations such that no agglomeration of active phases with the highest crystallinity was observed. The plasma treated sample showed better textural properties than untreated nanocatalyst. The main advantage of plasma was clearly observed on the stability of the nanocatalyst that the reduction the activity of untreated sample was more than two times of those for treated nanocatalyst. The plasma treated KOH/Ca12Al14O33-C exhibited no deformation of support structure and leaching of calcium component in the reaction medium against of untreated sample. Therefore, the plasma microwave hybrid synthesis method provides an excellent rout for preparation of surface modified nanocatalysts for biodiesel production with the highest activity and stability to decrease the production cost. (C) 2019 Elsevier Ltd. All rights reserved.