AbstractChip‐scale optical frequency combs have attracted significant research interest and can be used in applications ranging from precision spectroscopy to telecom channel generators and lidar systems. In the time domain, microresonator based frequency combs correspond to self‐stabilized soliton pulses. In two distinct regimes, microresonators are shown to emit either bright solitons in the anomalous dispersion regime or dark solitons (a short time of darkness in a bright background signal) in the normal dispersion regime. Here, the dynamics of continuous‐wave‐laser‐driven soliton generation is investigated in the zero‐group‐velocity‐dispersion regime as well as the generation of solitons that are spectrally crossing different dispersion regimes. In the measurements, zero‐dispersion solitons with multipeak structures (soliton molecules) are observed with distinct and predictable spectral envelopes that are a result of fifth‐order dispersion of the resonators. Numerical simulations and the analysis of bifurcation structures agree well with the observed soliton states. This is the first observation of soliton generation that is governed by fifth‐order dispersion, which can have applications in ultrafast optics, telecom systems, and optical spectroscopy.