Analogous with most modern cities, waste disposal is a pressing issue due to limited landfill and public filling (land reclamation) areas in Hong Kong in which construction and demolition (C&D) waste forms the major source. Concrete, apportioning the largest portion of C&D waste, has the greatest potential for recycling. However, the knowledge on micro-structural behavior of concrete waste is immature to give adequate details on the macro-behavior of concrete waste. This paper attempts to examine the problems of recycling old concrete by investigating the microstructure and phase transformation of the concrete samples collected from buildings with 46 and 37 years of services. From the results of FT-IR and SEM examination, it is found that there are a lot of pores at the near layers of aggregate where carbonation of the hardened cement paste (HCP) is high. The pores may be generated as a result of poor workmanship such as insufficient concrete mixing time, trapping of air voids beneath coarse aggregate, inappropriate water to cement ratio, and the microclimate conditions such as humidity that affects the demand on water from the aggregate during mixing.