In the field of Ziegler-Natta catalysis (ZNC), most of the previous works have been focused on the characterization of either catalyst surface or polymer microstructure but the combined studies of these two aspects are still limited. A clearer understanding concerning the isospecific nature of active sites on the donor-free TiCl3 - based catalyst has been presented in this work in terms of both surface characteristics of the catalyst and microstructure of polypropylene (PP) produced. Ti- and Al-species existing in the catalyst surface have been identified by high resolution X-ray photoelectron spectroscopic (XPS) and solid-state magic angle spinning nuclear magnetic resonance (Al-27 MAS NMR) techniques, respectively. Moreover, grinding effect on catalyst performance has been carried out to investigate the nature of active sites by particle size distribution (PSD) method. Microstructures of PPs produced using the surface characterized catalysts have been investigated by temperature rising elution fractionation (TREF), C-13 NMR and GPC methods. It can be demonstrated that the surface structure of catalyst is dominantly affected by the type of Al-alkyl cocatalyst used as well as the preparation method of catalyst whilst it precisely determine the nature of isospecificity of active sites and its distribution. Two different types of surface Ti+3-species have been identified on the catalyst surface depending on the different vacant coordination states of surface titanium species. On the other hand, Al-27 MAS NMR experiments have shown the presence of surface aluminum in four (Al-IV), five (Al-V) and six (Al-VI) coordination number of multiple environments. The states of surface Al-species are sensitive to coordination number and symmetry of the local environment around the aluminum nuclei. Higher isospecificity of active sites is seen to be related to the higher fulfilled coordinated states of surface Ti- and Al-species. (C) 2010 Elsevier Ltd. All rights reserved.