To control the pore size of silcia gel, formamide (FA), N,N-dimethyl formamide (DMF), polyethylene glycol (PEG) and polyacrylic acid (PAA) were added in the sol-gel process from starting solution with tetramethyl orthosilicate (TMOS). The gels were characterized using porosimeter, TG-DTA and SEM. As a result, the more contents of FA and PAA was increased the more gelation time was decreased, also the more contents of DMF and PEG was increased the more gelling time was increased. The mean pore size of gels was larger in the order of PAA, DMF, FA and PEG. And the mean pore size of porous silica glass was 59.0$AA$, 31.5$AA$, 29.9$AA$ and 29.0$AA$, respectively, heated at 75$0^{circ}C$/100$0^{circ}C$.