The evolutions of microstructure and phase transformation behavior of Cu-Al-Fe-Nb/Ta high-temperature shape memory alloys under the quenched and aged states were investigated in this study, including Cu-10wt.% Al-6wt.% Fe, Cu-10wt.% Al-4wt.% Fe-2wt.% Nb and Cu-10wt.% Al-4wt.% Fe-2wt.% Ta three types alloys. The obtained results show that after quenching, Cu-10wt.% Al-6wt.% Fe alloy exhibits two-phase microstructure of β′1 martensite + Fe (Al,Cu) phase; Cu-10wt.% Al-4wt.% Fe-2wt.% Nb alloy also has two-phase microstructure of (β′1 + γ′1 martensites) + Nb (Fe,Al,Cu)2 phase; Cu-10wt.% Al-4wt.% Fe-2wt.% Ta alloy is consisted of three-phase of (β′1 + γ′1 martensites) + Fe (Al,Cu,Ta) + Ta2(Al,Cu,Fe)3 phases. However, α (Cu) phase precipitates after aging for three alloys; and Fe (Al,Cu,Nb) phase is also present in Cu-10wt.% Al-4wt.% Fe-2wt.% Nb alloy. All the studied alloys exhibit complicated martensitic transformation behaviors resulted from the existence of two types martensites (β′1 and γ′1).