Over the past few decades, ultrahigh-performance concrete (UHPC) has been widely studied and applied because of its outstanding mechanical properties, such as its high strength and notable durability. However, because of its high cost and easy shrinkage cracking during early pouring in mass concrete construction, to reduce the cost of UHPC and reduce the cracks caused by early pouring, volcanic stone was used as a new type of UHPC coarse aggregate, while metakaolin (MK) was added to the system at the same time, and then two parameters, namely the volcanic rock particle size group and the MK dispersion ratio, were set. Scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetric (TG) microanalysis methods were used to reveal the influence of changes in the material microstructure, phase composition, material composition and crystallinity of the mineral composition on the compressive properties of the UHPC cubes. The results show that the mechanical “lock-in effect” of the structure formed by the volcanic rock holes and mortar can effectively improve the shear resistance of the UHPC–volcanic rock interface, and the compressive strength of the UHPC cubes increases with the volcanic stone’s particle size. When the MK dispersion ratio is less than 4%, the cube compressive strength of the UHPC and the contents of CaCO3 crystals, C-S-H gel and travertine in the UHPC increase with an increasing MK dispersion ratio. At an age of 28 days, compared with the addition of 1% MK, the addition of 4% MK increases the production of C-S-H gel and travertine in the UHPC matrix by 24.82%. When the MK dispersion ratio is 4%, the crystallinity values of the C-S-H gel, travertine and limestone in the UHPC are greater. Adding MK at a 4% dispersion ratio can promote the crystallization of limestone into a large amount of calcite, which can increase the strength of UHPC. On the one hand, the addition of volcanic coarse aggregate results in the retention of more free water and bound water; on the other hand, it also makes it difficult to crystallize CaCO3. The combined action of MK at a 4% dispersion ratio and volcanic rock significantly inhibits CaCO3 crystallization.