Zero thermal expansion (ZTE) behavior is rare but important for both fundamental studies and practical applications of functional materials. Until now, most available ZTE materials are either electrical insulating oxides or conductive metallic compounds. Very few ZTE materials exhibit the semiconductor feature. Here we report a ZTE in a semiconducting ferroelectric of 0.6PbTiO3-0.4Bi(Co0.55Ti0.45)O3-δ. Its unit cell volume exhibits a negligible change over a broad temperature range from room temperature to 500 °C. The ZTE is supposed to be correlated with the spontaneous volume ferroelectronstriction. Intriguingly, the present ZTE material also exhibits the semiconducting characteristic accompanied by negative temperature coefficient of resistance. The mechanism of electric conduction is attributed to the electronic hopping from one ion (Ti3+) to another (Ti4+). The semiconductor nature has also been confirmed by the noticeable visible-light absorption with the relatively lower band gap (Eg) value of 1.5 eV, while the ferroelectric property can be well-maintained with large polarization. The first-principles calculations reveal that the drastically narrowed Eg is related to the Co-Ti substitution. The present multifunctional material containing ZTE, semiconducting, and ferroelectric properties is suggested to enable new applications such as the substrate for solar conversion devices.