Abstract: This study used data from 140 National Directorate of Employment (NDE) assisted self-employed entrepreneurs and 104 non-assisted self-employed entrepreneurs to examine the operational mode of self-employment enterprises with a view to highlighting their potentials in poverty alleviation. The study was carried out in Ekiti State, Nigeria. A multi-stage random sampling technique was applied in the survey. Both primary and secondary data were used. Descriptive statistics, multivariate regression analysis and Chow test were employed to analyse the data collected. Regression analysis was used to show the effects of some socio-economic characteristics on the household income, proxy for poverty. Chow test was used to show a possible difference in poverty level between the NDE beneficiaries and non beneficiaries. Descriptive statistics reveals that 53% (majority) of the respondents were into vocational trades while 96% of the non-beneficiaries were able to raise the initial capital from friends and relatives. The majority of the beneficiaries started their businesses with capital between 31,000 and 70,000 while 53% of the non-beneficiaries commenced operations with the capital base less than 10,000. Within 5 years of operation, 76% of the beneficiaries were able to raise their capital base to between 101,000 and 400,000 while 70%s of the non-beneficiaries were unable to raise theirs to 101,000. Seventy five percent of the beneficiaries earned over 90,000 per annum while 67% of the other group earned less than 71,000 per annum. Regression analysis reveals that the main determinants of poverty in the study area are, initial capital (X₂), household size (X₃), present business value (X₆), number of household member working (X₈), household head educational status (X₉), years of experience (X₁₀) and number of apprentices (X₁₁). The Chow test shows that poverty level among the beneficiaries of the NDE programmes are lower than that of the non-beneficiaries. Some recommendations were made as to how poverty could be alleviated through self-employment enterprises.