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In order to precisely measure the diameters for obtaining the fineness of rolling raw silk, the physical features of raw silk are analyzed. By means of Fresnel principle, diffractions caused by different transparent raw silk filaments are analyzed and simulated. Image data of raw silk filament measured by digital CMOS camera are analyzed and processed for obtaining the precise diameters of the filament with the relative error of less than 1%. On the assumption of appropriate elliptic cross-section of the filament, the cross-section area is calculated as the fineness of the filament. Measurement experiments are carried out. Finally, some suggestions are proposed for photoelectric measuring the fineness of raw silk.