X-ray Timing and Polarimetry (XTP) telescope is proposed by using nested focusing optics with a large effective area for studies in the field of high energy physics (energy region of 1-30 keV). Highreflectance and low-stress W/Si multilayers are required for this telescope to improve the spectral response and maintain the figure quality of the mirrors simultaneously. In this paper, we focused on the study of stress and layer structure of W/Si periodic multilayers at different d-spacings (thickness of period), thickness ratios, and bilayer numbers. The results show that the stress of the multilayer increased from −73.3 to −465.5 MPa with increase in the d-spacing from 2.7 to 5.5 nm, while the change in the average interface width was negligible, from 0.31 to 0.36 nm. For the multilayers prepared with different thickness ratios of W, from 0.3 to 0.67 (d = 3.7 nm), the lowest stress appeared at the ratio of ∼0.46, and the average interface width was unchanged. The number of bilayers (N = 80-160) had negligible effects on both the layer structure and the stress, and the multilayers exhibited a very smooth surface morphology with a root-mean-square roughness of 0.19 nm. To further study the microstructural changes of the multilayer, X-ray diffraction measurements of the samples with different d-spacings and thickness ratios were performed. An increased crystallization along with phase changes were observed in the samples prepared with thicker W layers, which can increase the compressive stress of the multilayer.