The increase in heat generated by electronic components requires a need to expand the range of two-phase heat exchangers for thermal stabilization of the components. The efficiency of the two-phase systems (heat pipes, steam chambers) can be improved by using metal-fiber capillary-porous structures. Experimental studies for the conditions close to the operating conditions of heat pipes and vapor chambers described in known publications are rather incomplete. The aim of this study is to determine the boundary heat fluxes for water boiling on porous structures under capillary soaking, to investigate the influence of saturation pressure and structural parameters on the boundary heat fluxes, and to determine the optimal structural parameters of porous samples, i.e. such parameters that would allow the highest possible values of critical heat fluxes under given conditions. The authors investigate 0.3 and 0.5 mm thick capillary structure samples made of copper fibers with a diameter of 10 to 50 μm and a porosity range of 65—85%. The study has found that reducing the saturation pressure from 0.1 to 0.012 MPa leads to a decrease in the boundary heat flux values by 15—40%, depending on the effective pore diameters. The study allowed establishing that the maximum heat flux values are achieved for the samples with an effective pore diameter of 60 to 80 μm. It was also found that for the 0.5 mm thick samples, the boundary heat fluxes are 5—20% higher than for the 0.3 mm thick samples. The decrease in saturation pressure has been found to lead to a decrease in the range of two-phase heat exchange systems. For a number of samples, the authors have obtained the optimal effective pore diameters ensuring the highest critical heat flux values in the studied range.