A rigid body can be modelled as a system of N particles where the distance between any pair of them doesn't change. By definition, the center of mass is such that if it is the origin of the coordinate system: $\sum m_k\mathbf r_k = 0$. If we differentiate the equation with respect to time: $\sum m_k\mathbf v_k = 0 \implies \sum \mathbf p_k = 0$. The sum of the linear momentum is always zero in the frame of the COM. But there is a lot of freedom of movement of the individual particles compatible with the requirement that $\sum \mathbf p_k = 0$. That is the natural state of movement of a rigid body free of external forces and can be quite complex.
If we are initially in the frame of the COM, and an arbitrary net force is applied over the body for a small time $\delta t$, the new momentum configuration is: $\sum \mathbf p_k' = \sum \mathbf p_k + \sum \boldsymbol {\delta p_k} = \sum \boldsymbol {\delta p_k}$. As the sum of the linear momentum is always zero in the frame of the COM, that means: the COM has now in our frame a linear momentum $\boldsymbol{\delta p} = \sum \boldsymbol {\delta p_k}$.
In the particular case of all $\boldsymbol {\delta p_k}$ are equal, the state of movement of the body doesn't change except for the translation of the COM. But if it is not the case (an imbalanced external force), there are many possibilities. If all $\mathbf p_k$ were zero initially, (the OP question) it is perfectly possible that for some $k$, $\boldsymbol {\delta p_k}$ is momentarilly in a direction opposed to $\sum \boldsymbol {\delta p_k}$, the translational movement of the COM.