To quantify diffusion weighting and to calculate the diagnostically valuable “Apparent Diffusion Coefficient” (ADC) in MR-based “Diffusion-Weighted Imaging” (DWI), a standardized b-value is typically used. To avoid typical shortcomings of standard DWI, diffusion-weighted double-echo-steady-state (dwDESS) sequences were proposed, which don’t show geometrical distortions. Balanced bipolar dwDESS, in particular, provides high SNR and is robust against motion. However, a proper definition of the b-value equivalent to standard DWI is not yet well addressed. This study investigated an estimation for effective b-values in dwDESS based on approximation of the underlying signal model, which was verified in phantom and human measurements.