In the last several decades, Waste Electrical and Electronic Equipment (WEEE) reverse supply chain management has increasingly gained more attention due to the development of an environmental awareness, the rapid raise of e-wasted products and the EU regulations. In particular, although the new EU WEEE collection target has not been reached by many EU countries, several studies show that an optimized WEEE wastes management processes could represent a relevant way to achieve economic, environmental and social benefits expected by the adoption of circular economy approaches. According to this, the paper aims to evaluate the extent to which the current Italian organization of the WEEE management system and the related legislation are able to support the achievement of the targets defined by EU with a specific focus on the collection centers (CCs) which play a key role being the initial point of the WEEE reverse logistic cycle. An illustrative analysis based on the transition probability matrix regarding both the e-waste collecting performance and the distribution of collecting centers in the Italian provinces is illustrated. Furthermore, we have analyzed the presence of a correlation between the WEEE collection rate and the presence of the CCs in different provinces in order to better comprehend the role that can play both the investments in CC system and other soft measures in achieving the WEEE collection targets. Results show that the current Italian organization of the WEEE management system and the related legislations are not so effective in supporting the achievement of EU WEEE collection targets at the national level, although some geographical areas and provinces outperform the EU targets.