The effects of calcination temperature on the connectivity of pore networks of alumina and aluminium borate samples, prepared by coprecipitation methods and low-water sol–gel processes, have been investigated based on the percolation analysis of their nitrogen adsorption isotherms. The mean coordination number (Z) was determined with the aid of the recently proposed Seaton theory. Values of Z obtained with this method cover the range 2–3, implying a low connection of pores in all the examined porous samples. Thermal effects may increase or decrease Z values depending on the samples. On the other hand, Z values of aluminium borate samples obtained from the coprecipitation method were slightly larger than those from the sol–gel process. It was also found that for sol–gel processed samples, Z values of alumina were slightly larger than that of aluminium borate.