High-performance hydrogels with favorable mechanical strength, high modulus, sufficient ionic conductivity and freezing resistance have far-ranging applications in flexible electronic equipment. Nevertheless, it is challenging to combine admirable mechanical properties and high ionic conductivity into one hydrogel. Herein, a facile strategy was developed for the preparation of the hydrogel with excellent strength (1.45 MPa), super Young's modulus (8.85 MPa) and high conductivity (1.47 S/m) using starch and poly(vinyl alcohol) (PVA) as raw materials. The starch/PVA/Gly/Na3Cit (SPGN) gel was firstly cross-linked by crystalline regions of PVA upon freezing-thawing cycles. It was further immersed in the saturated Na3Cit solution to enhance the interaction between the substrates through the salting-out effect. The effect of soaking time on the crystallinity, intermolecular interactions, mechanical and electrical properties of SPGN gel was demonstrated by X-ray diffraction, Fourier transform infrared spectroscopy, tensile and impedance testing measurements. The introduction of glycerol and Na3Cit also endowed SPGN gels with favorable anti-freezing properties. The SPGN gel could maintain high mechanical flexibility and ionic conductivity at −15 °C.