Gas entrainment may cause pressurization deterioration and even failure of pumps under conditions of high inlet gas volume fraction (GVF). When the inlet GVF increases to a critical value, an obvious deterioration performance of pump occurs. Air-water pressurization performance and inlet critical GVFs of a centrifugal multiphase pump are investigated experimentally under different inlet pressures and gas-liquid flow rates. To determine the first and second critical GVFs, a new method is proposed by computing the local extreme points of the second derivative of performance curves. New prediction correlations for two critical GVFs are established with relative errors lower than ±10% and ±8%. Boundaries of three different flow patterns and the transition flow rates are determined and presented by critical GVFs on the flow pattern diagram. Moreover, boundaries of maximum pressurization are determined by performance curve clusters and a power function correlation of gas-liquid flow rates when reaching the maximum pressurization is established. With the increase of inlet pressure from 1MPa to 5MPa, two-phase pressurization performance is significantly increased; occurrences of pressurization deterioration are obviously delayed with the first and second critical GVFs increasing by maximums of 8.2% and 7.1%.