The electron correlations as triggered by on-site Coulomb repulsion within correlated vanadium dioxide (VO2) open up an emerging paradigm to explore new electronic phases and promising device applications. Apart from correlated electrical transport, the thermoelectric thermopower (S) of VO2 also undergoes abrupt variation across the critical temperature (TMIT) that sheds lights on the potential thermoelectric functionality. Nevertheless, bridging bi-functionality of VO2 associated with the thermistor and thermoelectric properties is still restricted by the limitation in improving the absolute magnitude of S and temperature coefficient of resistance (TCR). Herein, we demonstrate the widely adjustable metal–insulator transition (MIT) behavior and overlooked thermoelectric performance for Ti-substituted VO2 pellets that enable the bi-functionality strategy as combined with thermistor and thermoelectric properties. As-achieved tunable TMIT while maintaining large |TCR| is herein achieved for Ti-substituted VO2 pellets that enables practical device applications near room temperature. Apart from the well-known MIT functionality, we reveal the overlooked thermoelectric properties for VO2 via coherently co-sintering with TiO2 that introduces a new freedom (thermopower). Specifically, the largely enhanced thermopower observed for insulating V1−xTixO2 exceeds the one for pristine VO2 by five times, while the thermoelectric power factor for its metallic phase is comparable to typical organic or oxide thermoelectric materials. The presently achieved thermistor and thermoelectric bi-functionality (e.g., |S| > 100 μV/K and |TCR| > 1 K−1) for Ti-substituted VO2 pellets extends the horizons in material designs that combines such a bi-functionality to achieve both the passive and active sensing for improving the accuracy in thermal perturbations of VO2 bulk as infrared detectors near room temperature.