The modified sol‐gel method using ethylenediaminetetraacetic acid as a chelating agent to prepare high‐Tcsuperconducting Bi‐Pb‐Sr‐Ca‐Cu oxides is reported. Results revealed that the desirable Bi‐based compounds can be acquired by such a process with a high percentage of the 110 K phase and aTc(zero) of 108 K. On the other hand, a new method is proposed to quantitatively evaluate the volume fraction of the 110 K phase in Bi‐based superconducting materials, mainly composed of 85 and 110 K phases. That is a lever‐rule type of relation,V= (Y– 29.07°)/ (28.81°– 29.07°), whereVis the volume fraction of the 110 K phase andY= 2θfor the X‐ray diffraction peak emerging at about 29° with a CuKα radiation source and 28.81°Y29.07°. The volume fraction of the 2223 phase estimated in this way is more reliable than that estimated by measuring the area ratios of XRD peaks and it is expected to be even more reliable than those derived from conventional method