Here we describe the Primitive Object Volatile Explorer (PrOVE), a smallsat mission concept to study the surface structure and volatile inventory of comets in their perihelion passage phase when volatile activity is near peak. CubeSat infrastructure imposes limits on propulsion systems, which are compounded by sensitivity to the spacecraft disposal state from the launch platform and potential launch delays. We propose circumventing launch platform complications by using waypoints in space to park a deep space SmallSat or CubeSat while awaiting the opportunity to enter a trajectory to flyby a suitable target. In our Planetary Science Deep Space SmallSat Studies (PSDS3) project, we investigated scientific goals, waypoint options, potential concept of operations (ConOps) for periodic and new comets, spacecraft bus infrastructure requirements, launch platforms, and mission operations and phases. Our payload would include two low-risk instruments: a visible image (VisCAM) for 5-10 m resolution surface maps; and a highly versatile multispectral Comet CAMera (ComCAM) will measure 1) H2O, CO2, CO, and organics non-thermal fluorescence signatures in the 2-5 μm MWIR, and 2) 7-10 and 8-14 μm thermal (LWIR) emission. This payload would return unique data not obtainable from ground-based telescopes and complement data from Earth-orbiting observatories. Thus, the PrOVE mission would (1) acquire visible surface maps, (2) investigate chemical heterogeneity of a comet nucleus by quantifying volatile species abundance and changes with solar insolation, (3) map the spatial distribution of volatiles and determine any variations, and (4) determine the frequency and distribution of outbursts.