In sub-Saharan Africa, young women engaged in relationships with multiple partners in order to gain material benefits play a key role in local HIV dynamics. This paper is based upon field observations and interviews with 38 young women who live along the Angolan-Namibian border. In the last 10 years, rapid urbanisation has attracted migrants in search of opportunities to do business in the region. Our findings show that sexual-affective economic networks reflect these socioeconomic changes. Women, particularly those from particular ethnic groups and/or from Namibia, with low levels of formal education and social support are often excluded from the labour market and turn to emotional-sexual male-centred networks for material and financial benefits. Men in these networks tend to be older, have higher socioeconomic status and greater geographic mobility. This 'capitalisation' of intimate relationships is material and symbolic; it enables women to acquire goods and access to services identified with an urban and globalised lifestyle. It is also emotional because relationships include affection and pleasure. Engaging in these relationships involves some social risks (bad reputation, family rejection, discrimination and violence), but maintaining ties often takes priority over safer sex and social sanctions.