In this study, for restoration of ecological systems in buildings, porous vegetation red clay green roof blocks were designed for performance evaluation. Blast furnace slag (BFS; fine aggregates (agg.)), coarse aggregates, polyvinyl alcohol (PVA) fiber (hydrophilic fiber), and red clay (ecofriendly additive material) were applied to the construction of the porous vegetation red clay green roof blocks. A decrease in cement use is one way of reducing carbon emissions. To increase the water retentivity and the efficiency of roof vegetation blocks, blast furnace slag aggregates with excellent water absorptivity and polyvinyl alcohol fiber with a water absorption rate above 20% were added. In particular, the addition of polyvinyl alcohol fiber prevents performance reduction of the green roof vegetation blocks during freezing and melting in winter. Compressive strength, void ratio, and unit-mass tests were conducted to evaluate the performance of the roof vegetation blocks. After their application to roof vegetation, the effect of water purification was evaluated. According to the experimental results, the mix that satisfies the target performance of green roof vegetation blocks (compression strength above 8 MPa, void ratio above 20%, unit mass 2.0 kg/cm3 or below) is: cement = 128.95 kg/m3, BFS = 96.75 kg/m3, red clay = 96.75 kg/m3, water = 81.50 kg/m3, BFS agg. = 1450 kg/m3, PVA fiber = 1.26 kg/m3. The green roof vegetation blocks were designed using the mix that satisfied the target performance. To find the amount of attainable water due to rainfall, a rainfall meter was installed after application of the roof vegetation to measure daily rainfall and calculate the amount of attainable water. The results show that, for 1 mm of rainfall, it is possible to attain about 0.53 L of water per 1 m2. In addition, the water quality of effluents after application of roof vegetation was analyzed, and the results satisfied Class 4 of the River-life Environmental Standard for Availability of Agricultural Water.