The separate collection of individual recyclable waste materials is the basis for any recycling process. This produces important advantages, especially in terms of resource savings. This paper investigates the drivers of the separate collection process of recyclable materials (i.e., organic, paper, glass, plastic) and its total in the 103 Italian provinces (NUTS-3), in the years 2004–2011. Results show that the pillars of institutional quality (such as, voice and accountability, rule of law and regulatory quality), value added per capita and participation to ecological associations are important factors for an effective implementation of the waste separation process. In particular, these factors do matter for an effective collection of organic waste, paper, glass and plastic. Furthermore, the analysis shows marked differences among macro-areas (North, Central and Southern Italy). Policy considerations are discussed.