SEC and on-line Fourier transform infrared spectroscopy analysis have been combined to study branching profiles from the Phillips Cr/silica catalyst. For the first time, catalyst and reactor variables have been shown to affect the overall level and distribution of branches in polyethylene copolymers. Branching profiles from various chromium catalysts have been shown to vary from highly concentrated in the low MW end, to uniformly distributed over all of the MW range. Activation temperature and the presence of titania were highly influential. These observations, which have been used to gain insight into the chemistry of Cr/silica, explain much of the catalyst behavior that has for decades been used to optimize polymer properties. Trends in ESCR, impact resistance, and other physical characteristics, which were long attributed to changes in MW distribution, can now be seen to also be due in large part to changes in the branching profile. This knowledge should be of value in designing future resins. (c) 2007 Wiley Periodicals, Inc.