The objective of the study was to examine the peculiarities of practical application of the effective regulatory and legal documents used for occupational risk assessment. Regulatory and legal acts, methodological and guiding documents as well as state standards regulating occupational risk assessment have been analyzed; the application of certain methodologies of occupational risk assessment for employees of primary occupations engaged in copper and zinc ores extraction and processing was tested by two methods, i.e., the matrix method using the RiskProf online service and the method according to R 2.2.3969—23. The final assessment of the occupational risk of health disorders of employees of primary occupations was performed by the matrix method, considering a hazard (hazardous event), severity, and the probability of possible events. For all professional groups, the occupational risk assessed by the matrix method corresponded to the average level. The occupational risk assessment of employees’ health disorders in accordance with R 2.2.3969—23 demonstrated that the risk among employees of various occupations has been very high. The application of two methods of occupational risk assessment provided significant inconsistency in results. The risk analysis based on the retrospective data including earlier implemented risks in the form of occupational illnesses provided a more negative forecast; whereas the detected risks require a higher prioritization when developing measures to improve working conditions. As a result of the integrated occupational risk assessment, a very high risk category has been established for sinkers on hand drills (5 points), high for sinkers of drilling rigs and drivers of loading and delivery machines (4 points); for the other employees, the risk category complied with the average level. The obtained results demonstrate that only the use of both methodologies has ensured an objective occupational risk assessment considering expected (potential) and implemented risks.