Investigation of arbitrary amplitude nonlinear ion-acoustic solitary waves which accompany collisionless positive–negative ion plasmas with high-energy electrons (represented by kappa distribution) is presented. Arbitrary amplitude solitary waves are investigated by deriving an energy-integral equation involving a Sagdeev-like pseudopotential. The existence regions of solitary pulses are, defined precisely, modified by the superthermality of energetic electrons. Furthermore, numerical calculations reveal that both compressive and rarefactive pulses may exist for negative ion mass groups in Titan's atmosphere. The superthermality of energetic electrons are found to modify the existence domains of large amplitude ion-acoustic waves in Titan's atmosphere. The dependence of solitary excitation characteristics on the superthermal parameter, the negative ion concentration, the positive-to-negative ions mass ratio, and the Mach number have been investigated. The present study might be helpful to understand the excitation of fully nonlinear ion-acoustic solitary pulses that may appear in the interplanetary medium and/or in the astrophysical plasmas in general.