High temperature triggered multiple-shape memory poly(benzoxazole-co-imide)s with adjustable properties were prepared via facile random copolymerization 3,3′,4,4′-biphenyltetracarbolylic dianhydride (BPDA) with two different diamine of 4,4′-oxydianiline (ODA) and 5-amino-2-(4-aminobenzene) benzoxazole (BOA). The effect of polybenzoxazole on the molecular packing, physical properties and shape memory behaviors of poly(benzoxazole-co-imide)s was investigated systematically. The incorporation of polybenzoxazole into polyimides endows better mechanical properties, higher chain packing, broad glass transition temperature and excellent tunable dual-shape memory behaviors with shape fixity above 98% and shape recovery up to 98%. Besides, multiple-shape memory effects with high switching temperature are first achieved in poly(benzoxazole-co-imide)s, and the multiple-shape memory could be adjusted by choosing the two different switching temperatures. Lastly, the potential mechanism of multiple-shape memory behaviors of poly(benzoxazole-co-imide)s are suggested.