In order to further study the internal relationship between the microscopic pore characteristics and macroscopic mechanical properties of cemented tailings backfill (CTB), in this study, mine tailings and ordinary Portland cement (PC32.5) were selected as aggregate and cementing materials, respectively, and different additives (anionic polyacrylamide (APAM), lime and fly ash) were added to backfill samples with mass concentration of 74% and cement–sand ratios of 1:4, 1:6 and 1:8. After 28 days of curing, based on the uniaxial compressive strength test, nuclear magnetic resonance (NMR) porosity test and the fractal characteristics of pore structure, the relationships of the compressive strength with the proportion and fractal dimension of pores with different radii were analyzed. The uniaxial compressive strength prediction model of the CTB with the proportion of harmless pores and the fractal dimension of harmful pores as independent variables was established. The results show that the internal pores of the material are mainly the harmless and less harmful pores, and the sum of the average proportions of the two reaches 73.45%. Some characterization parameters of pore structure have a high correlation with the compressive strength. Among them, the correlation coefficients of compressive strength with the proportion of harmless pores and fractal dimension of harmful pores are 0.9219 and 0.9049, respectively. The regression results of the strength prediction model are significant, and the correlation coefficient is 0.9524. The predicted strength value is close to the actual strength value, and the predicted results are accurate and reliable.