Electrostatic solitons in an unmagnetized pair-ion plasma comprising adiabatic fluid positive and negative ions and non-isothermal electrons are investigated using both arbitrary and small amplitude techniques. An energy integral equation involving the Sagdeev potential is derived, and the basic properties of large amplitude solitary structures are investigated. Various features of solitons differ in different existence domains. The effects of ion adiabaticity, particle concentration, and resonant electrons on the profiles of Sagdeev potential and corresponding solitary waves are investigated. The generalized Korteweg-de Vries equation with mixed-nonlinearity is derived by expanding the Sagdeev potential. Asymptotic solutions for different orders of nonlinearity are discussed for solitary waves. The present work is applicable to understanding the wave phenomena and associated nonlinear electrostatic perturbations in pair/bi-ion plasmas which may occur in space and laboratory plasmas.