Endmember estimation plays a key role in hyperspectral image unmixing, often requiring an estimation of the number of endmembers and extracting endmembers. However, most of the existing extraction algorithms require prior knowledge regarding the number of endmembers, being a critical process during unmixing. To bridge this, a new maximum distance analysis (MDA) method is proposed that simultaneously estimates the number and spectral signatures of endmembers without any prior information on the experimental data containing pure pixel spectral signatures and no noise, being based on the assumption that endmembers form a simplex with the greatest volume over all pixel combinations. The simplex includes the farthest pixel point from the coordinate origin in the spectral space, which implies that: (1) the farthest pixel point from any other pixel point must be an endmember, (2) the farthest pixel point from any line must be an endmember, and (3) the farthest pixel point from any plane (or affine hull) must be an endmember. Under this scenario, the farthest pixel point from the coordinate origin is the first endmember, being used to create the aforementioned point, line, plane, and affine hull. The remaining endmembers are extracted by repetitively searching for the pixel points that satisfy the above three assumptions. In addition to behaving as an endmember estimation algorithm by itself, the MDA method can co-operate with existing endmember extraction techniques without the pure pixel assumption via generalizing them into more effective schemes. The conducted experiments validate the effectiveness and efficiency of our method on synthetic and real data.