Interfacial water structures have been investigated in an ambient environment between two silica surfaces using a newly developed cantilever based optical interfacial force microscope (COIFM). As the gap distance decreases between the tip and the substrate, a remarkable oscillatory behavior is oberved in normal and friction forces. Our further analysis suggests that water molecules confined between tip and substrate in an ambient environment form a bundle of water chains through hydrogen bonding. Each chain length is analyzed by a model called “freely jointed chain” (FJC) model in which the individual segments can rotate freely. The bundle of water chains experiences multiple layering transitions (without single layer transition) from l = 36 diameters to l=12 diameters as the tip approaches the surface. The analysis shows that the number of links (l) decreases by 5,4,3,3,3,3,4,5 in water diameters. The result indicates that, as the gap between the tip and the substrate decreases, the interfacial water molecules favor multilayer transitions to stepwise, single layer transitions. The multilayer transitions consist of a sequential reduction of total chain length by integer number of water diameters. The loss of one water diameter in overall chain length represents a highly cooperative transition, whereas the loss of two additional water diameter along the sigmoidal shape is reminiscent of a well-known two state transition. As a model to describe these transitions, a kink is introduced in the chain by rotating one water molecule 90 degrees while maintaining the number of hydrogen bonds in the chain. The other remaining molecules still follow the freely jointed chain model.