Machine tool accuracy is greatly influenced by geometric and thermal errors that cause positioning deviations within its working volume. Conventionally, these two error sources are treated separately, with distinct procedures employed for their characterization and correction. This research proposes a unified volumetric error compensation approach in terms of a calibration procedure and error compensation model, which considers geometric and thermal errors as a single error source that exhibits temporal variation primarily due to changes in the machine’s thermal state. Building upon previous works that introduced a fully automated volumetric calibration procedure capable of characterizing the variation in volumetric error over time, this study extends this methodology, incorporating multiple temperature sensors distributed throughout the machine and generating a digital twin based on a volumetric error compensation model capable of predicting and compensating for the volumetric error over time at any point in the workspace, using temperature measurements and axis positions as inputs. This methodology is applied to a medium-sized milling machine tool. The digital twin is trained and validated on volumetric calibration tests, wherein various controlled heat sources are employed to induce thermal variations while measuring the temperatures in the machine.