Silver nanoclusters capped by hyperbranched polyethylenimine (PEI) have been developed as a highly sensitive fluorescent and colorimetric pH sensor. The probe responds rapidly to pH fluctuations and has such absorption characteristics that the color changes from the colorless or a nearly colorless state to a colored state with increasing acidity, so PEI-capped Ag nanoclusters could be used as a color indicator for colorimetric pH detection. Quantitatively, the fluorescence intensity of PEI-capped Ag nanoclusters exhibits a linear fashion over the pH range of 5.02-7.96 and increases by around 10-fold approximately with greater fluorescence at higher pH values. The repulsion development and conformational change of PEI with decreasing pH induce the aggregation of Ag nanoclusters, leading to an obvious color change and fluorescence quenching of Ag nanoclusters at low pH values. As expected, the pH probe is also sensitive to the different buffer solutions, except for those containing some anions that could react with Ag nanoclusters. Besides, the ionic strength of the buffers has a little influence on the pH-responsive behavior. Our pH sensor with nanoscaled physical dimensions would be a promising candidate in the applications in biological, medical, and pharmaceutical fields.