The use of functionalized components in cement-based composites (CBC) is an innovative way to provide novel material’s capabilities. Carbon-based additions and fibers can modify electrical properties of CBC, such as piezoresistivity (PZR). PZR enables a new intrinsic capacity of CBC, relating the variation of material’s electrical resistance to material’s stress when subjected to external loads, successfully transforming CBC into a self-sensing material that can be used for Structural Health Monitoring (SHM). This study aims to evaluate the use of carbon fibers of biological sources (CF-BIO), obtained from lignin as raw material, which is a sustainable alternative to petroleum carbon fibers (CF-PAN), due to its natural origin and lower environmental impact. Fiber content required for achieving PZR capacity of CBC has been already defined for CF-PAN. The variation of electrical and piezoresistive properties as an effect of self-sensitive capacity were tested. These measurements were be used to calculate the fractional change resistivity (FCR) and the sensitivity rate of the material (Csens).