In this article, a Bi4π counting method comprised of Bi4π counter and a new fundamental measurement method was described, which can measures rather more radionuclides and can achieve accuracy of 0.03% to 0.06% (1σ), in principle. The correctness of this method is demonstrated by measurements of ⁶⁰Co sources which results of activities compared with 4π β-γ coincident method are in agreement within the measurement errors, and it is readily achieved to accuracy of 0.2%. Finally, the range of the applications for this Bi4π counting method among one hundred or more important radionuclides is also discussed.