Detonation nanodiamond (DND) is the smallest class of diamond nanocrystal capable of hosting various color centers with a size akin to molecular pores. Their negatively charged nitrogen-vacancy center (NV−) is a versatile tool for sensing a wide range of physical and even chemical parameters at the nanoscale. The NV− is, therefore, attracting interest as the smallest quantum sensor in biological research. Nonetheless, recent NV− enhancement in DND has yet to yield sufficient fluorescence per particle, leading to efforts to incorporate other group-IV color centers into DND. An example is adding a silicon dopant to the explosive mixture to create negatively charged silicon-vacancy centers (SiV−). In this paper, we report on efficient observation (∼50% of randomly selected spots) of the characteristic optically detected magnetic resonance (ODMR) NV− signal in silicon-doped DND (Si-DND) subjected to boiling acid surface cleaning. The NV− concentration is estimated by continuous-wave electron spin resonance spectroscopy to be 0.35 ppm without the NV− enrichment process. A temperature sensitivity of 0.36K/Hz in an NV− ensemble inside an aggregate of Si-DND is achieved via the ODMR-based technique. Transmission electron microscopy survey reveals that the Si-DNDs core sizes are ∼11.2 nm, the smallest among the nanodiamond’s temperature sensitivity studies. Furthermore, temperature sensing using both SiV− (all-optical technique) and NV− (ODMR-based technique) in the same confocal volume is demonstrated, showing Si-DND’s multimodal temperature sensing capability. The results of the study thereby pave a path for multi-color and multimodal biosensors and for decoupling the detected electrical field and temperature effects on the NV− center.