Poor air quality and environmental pollution remain some of the main etiological factors leading to cancers and cancer-related deaths worldwide. As a result of human activities, deleterious airborne chemicals can be dispersed not only in the environment but also released in occupational environments and industrial areas. Air pollutants and cancer links are now established through various oxidative stress-related mechanisms and related DNA damages. Generally, ambient and indoor air pollutants have been understudied in sub-Saharan Africa (SSA) compared to other regions in the world. Our study not only highlights the deleterious effects of air pollutants in these developing countries, but it has strived to examine the trends and correlations between cancers and some air pollutants—carbon dioxide, other greenhouse gases, PM2.5, and human development index—in some SSA countries, where recent cancer burdens were reported as high. Our results showed strikingly higher yearly trends of cancers and above-mentioned air pollutant levels in some sub-Saharan countries during 2005–2020. Relative risks (RR) of these air pollutants-related cancer case rates were, however, below, or slightly above 1.0, or not statistically significant possibly due to other responsible and confounding factors which were not considered in our analyses due to data unavailability. We recommend new approaches to monitoring, minimizing, and creating awareness of the trends of hazardous air pollutants in sub-Saharan Africa, which will help ameliorate cancer prevalence and support the reduction in air pollution levels within regulatory limits, thereby relieving the cumulative burdens of cancers. Utilization of the findings from the study will support large-scale public health and health policy efforts on cancer management through environmental stewardship in SSA countries having the poorest outcome and the shortest survival rates from cancers.