Skew convolution semigroups play an important role in the study of generalized Mehler semigroups and Ornstein-Uhlenbeck processes. We give a characterization for a general skew convolution semigroup on real separable Hilbert space whose characteristic functional is not necessarily differentiable at the initial time. A connection between this subject and catalytic branching superprocesses is established through fluctuation limits, providing a rich class of non-differentiable skew convolution semigroups. Path regularity of the corresponding generalized Ornstein-Uhlenbeck processes in different topologies is also discussed.