This study investigates the theoretical aspects of mass transport at the surface of a twin semicircular electrodiffusion probe tailored to measure the magnitude and direction of near-wall fluid flows. A critical aspect of this research is the development of a theoretical framework that facilitates experimental measurements by analytically relating measured electric currents to the wall shear stress vector. Central to the study is the derivation of analytical expressions for the mass transfer coefficients of the front and rear segments of the probe, which are essential for quantifying near-wall hydrodynamics. Validation of these analytical relations is achieved through numerical solutions of the convection–diffusion equation, providing a robust confirmation of the underlying theory. A comprehensive procedure for experimental data processing is proposed, taking into account both frontal and reverse flow conditions across the probe. In addition, a sensitivity analysis of the twin semicircular probe is performed. This analysis focuses on the response of current ratios to changes in the flow direction, an aspect critical to understanding the operational performance of the probe. The results of this analysis are compared to the characteristics of two-segment strip probes, highlighting the distinct sensitivity nuances of the twin semicircular probe. Our findings provide insight into the optimal application of this probe in various fluid dynamics scenarios.