Understanding the phase behavior of PEGylated phosphocholine membranes is becoming increasingly important in many biomedical applications. Here, we used binary mixtures of phosphocholines and PEG-phospholipids in monolayers on phosphate buffered saline as ideal models of PEGylated phosphocholine membranes. Several phase states and transitions between homogeneously mixed and completely immiscible phases have been visualized in these mixtures by epifluorescence microscopy, which is neither predicted nor easily explained by the existing interpretive schemes. The results of our study suggest that the phase state of PEGylated phosphocholine membranes may drastically vary depending on factors such as aliphatic chain length on phosphocholines and PEG-phospholipids, PEG content, and temperature. These findings are summarized in phase drawings and diagrams to demonstrate a striking variety of possible phases. The diagrams can also be instrumental in predicting the phase state of PEGylated phosphocholine membranes, in particular under physiological conditions.