Fiber-reinforced concrete (FRC) is an attractive alternative to traditional steel bar-reinforced concrete structures, as evidenced by the constantly increasing market consumption of structural fibers for this purpose. In spite of significant research dedicated to FRC, less attention has been given to the effects of low temperatures on the mechanical properties of FRC, which can be critical for a variety of structural typologies and regions. With this in mind, an experimental program was carried out to assess the flexural behavior of macro-synthetic fiber-reinforced concrete (MSFRC) at different temperatures (from 20 °C to −30 °C) by means of three-point bending notched beam tests. The tested MSFRCs were produced by varying the content of polypropylene fibers (4 and 8 kg/m3). The results proved that the flexural strength capacity of all MSFRCs improved with decreasing temperature. Finite element analyses were then used to calibrate constitutive models following fib Model Code 2010 guidelines and to formulate empirical adjustments for taking into account the effects of low temperatures. The outcomes of this research are the basis for future experimental and numerical efforts meant to improve the design of MSFRCs subjected to low temperatures during service conditions.