Charcoal is a popular form of biofuel embraced for domestic and industrial purposes. However, the use of Charcoal has some associated challenges, such as the required charcoal pot and setting it into the fire at first by using Charcoal-Ignition-Aiders (CIA) (e.g. discarded paper, nylon, rubber, plastics, petrol, the residue of processed palm oil, maise cob, wood, and kerosene). Coupled with the chemical properties of Charcoal, the resulting gases from CIA are capable of polluting the environment with perceived Adverse-Health-Implications (AHI) on the ecosystem. Therefore, this study conducted a safety assessment of charcoal biofuel usage and the effects of common CIA on combustion indices. This study followed standard methods and the use of peculiar equipment. This study established that Charcoal is commonly used in the studied area because it is cheap, readily available and requires less technical know-how. Considering the combustion indices, using paper as a CIA generated the lowest carbon monoxide (CO) value, 28.1 ppm, with 3,434.54 ppm volatile organic compound, VOC. Compared with the ACGIH standard permissible exposure level of ≤ 30 ppm, the paper gave a lesser CO value of 28.10 ppm among all the CIA. At the same time, all the CIA recorded higher VOC compared with EPA standard permissible exposure level of ≤ 15 ppm. ANOVA analysis conducted on the socio-demographic profile of the respondents, cooking attributes of the respondents, and use of charcoal pot types by the respondents in Zone 1, Zone 2, and Zone 3 gave p-values of 0.032, 0.028, and 0.039, respectively. These imply significant differences within the zones in each of the indices. The average energy content reported for charcoals sourced from oak trees, afara, obeche, mahogany, and iroko woods is 3,2149 kJ/kg compared to the lower ones. Therefore, this study recommended using these charcoals alongside discarded paper as CIA because they are a better combination to reduce AHI.