Maize and its products are most often prone to fungal contamination especially during cultivation and storage by toxigenic fungi. Aflatoxicosis still persist in Ghana despite the numerous education on several ways of its prevention at the farm as well as its adverse health implications which are food safety concerns. A random assessment and human risk analysis was conducted on 90 maize (72 white and 18 colored) samples from markets across all the regions of Ghana. Total aflatoxins (AFtotal) and the constitutive aflatoxins (AFB1, AFB2, AFG1, and AFG2) were analyzed by High-Performance Liquid Chromatography (HPLC). Out of a total of ninety (90) samples investigated, 72 (80%) tested positive for AFB1 and the contamination levels ranged from 0.78 ± 0.04 to 339.3 ± 8.6 µg kg−1. Similarly, AFG2 was detected in only 14 (15.5%) samples, and their values ranged between 1.09 ± 0.03 and 5.51 ± 0.26 µg kg−1 while AF total ranged between 0.78 ± 0.04 and 445.01 ± 8.9 µg kg−1 constituting approximately 72 (80%). Limits of AFB1 and total aflatoxins (AFtotal) for the Ghana Standards Authority (GSA) (5 and 10 µg kg−1) and the European Food Safety Authority (EFSA) (2 and 4 µg kg−1), were used as checks. A total of 33 (41.25%) samples were above the limits for both. Risk assessments recorded for Estimated Daily Intake (EDI), Hazard Quotient (H.Q), Hazard Index (H.I), Margin of Exposure (MOE), av. Potency, and population risks ranged 0.087–0.38 μg kg−1 bw day−1, 1.5–6.9, 0.0087–0.38, 3.64–12.09, 0–0.0396 ng Aflatoxins kg−1 bw day−1 and, 3.5 × 10–1–0.015 respectively for total aflatoxins. While ranges for aflatoxins B1 (AFB1) recorded were 0.068–0.3 μg Kg bw−1 day−1, 2.43–10.64, 0.0068–0.030, 4.73–20.51, 0–0.0396 ng Aflatoxins kg−1 bw day−1 and, 2.69 × 10–3–0.012 for Estimated Daily Intake (EDI), Hazard Quotient (H.Q), Hazard Index (H.I), Margin of Exposure (MOE), Av. potency, and population risks respectively. It was deduced that although there was some observed contamination of maize across the different ecological zones, the consumption of maize (white and colored) posed no adverse health effects on the population of Ghana since computed H.I was less than 1 (< 1).