In the present study, we synthesized nitrogen-pivot 16-crown-5 lariat (1) and investigated the thermodynamics of the complexation with aza-16-crown-5 lariat in acetonitrile of light lanthanoid(III) nitrates (Ln = La, Ce, Pr, Nd, Sm, Eu, and Gd), using titration calorimetry. The thermodynamic parameters for the complexation of light lanthanoid nitrates with aza-16-crown-5 lariat, together with those for 16-crown-5 (3) and the lariat ether (2), will serve our further understanding of this thermodynamically less investigated area of crown ether chemistry. It is another point of interest to examine the scope and limitations of the lariat effect with the relatively flexible N-pivot lariat ether from the thermodynamic point of view. 33 refs., 2 figs., 1 tab.