A new sol-gel silica material based on tetramethylammonium silicate (TMAS) is reported here. Both xerogels and aerogels were produced by gelling a solution of 18.7 wt% TMAS using a series of esters. The gelation kinetics was controlled by varying the type and concentration of the ester. The super-critically dried TMAS aerogel was seen to have a larger pore size distribution with high porosity (>90%). In contrast, the conventionally dried gel showed a narrow distribution of mesopores, indicating its potential as a host matrix for protein encapsulations and catalysts.