Aflatoxin contamination in foods is a vital health challenge for low and middle-income countries in subtropical regions. Maize (Zea mays L.), a staple food most widely grown in Africa including Ghana, and extensively consumed as much as three times per day, is a source of aflatoxin contamination owing to its susceptibility to fungal infection. Aflatoxin levels were checked against international (European Commission, EC) and local (Ghana Standards Authority, GSA) standards, and health risks associated with maize sampled from the Volta Region (Hohoe, Ho, Battor Dugame, and Keta) of Ghana were determined. Total aflatoxins (totalAFs) and the constituent aflatoxins (AFB1, AFB2, AFG1, and AFG2) were measured with High-Performance Liquid Chromatography (HPLC) with a Fluorescence Detector (FLD). Intake and Risk assessments were also conducted using deterministic models prescribed by the Joint FAO/WHO Expert Committee on Additives (JECFA). The degree of occurrence of aflatoxins was observed to be in decreasing order of AFG2 < AFG1 < AFB2 < AFB1 and were within the ranges of 0.78 ± 0.04 $$-$$
-
234.73 ± 3.8 µg/kg, 0.47 ± 0.03 $$-$$
-
21.6 ± 0.33 µg/kg, 1.01 ± 0.05 $$-$$
-
13.75 ± 1.2 µg/kg and 0.66 ± 0.06 $$-$$
-
5.51 ± 0.26 µg/kg respectively. Out of the 100 samples analyzed for total aflatoxins (totalAFs), 68 (68%) exceeded the limits of EC and were of range 4.98 ± 0.6 $$-$$
-
445.01 ± 8.9 µg/kg whereas 58 (58%) and ranged between 12.12 ± 1.4 $$-$$
-
445.01 ± 8.9 µg/kg exceeded GSA limits. Intake and risk assessments of total aflatoxins (totalAFs) for infants, toddlers, children, adolescents, and adults in the Volta Region were; 0.037–1.14 µg/kg bw/day, 0.35–10.81, and 1.47 -45.14 cases/10,000 person/yr respectively for Estimated Daily Intake (EDI), Margin of Exposure (MOE), and Cancer Risks. It was inferred that the consumption of maize posed potential adverse health effects on all age categories studied because all calculated MOE values were less than 10,000.