Exceptional challenges have confronted the rational design of colorimetric sensors for saturated aliphatic hydrocarbons (SAHCs). The main reasons for this difficulty are the extremely nonpolar nature of these targets and their lack of functional groups that can interact with probes. By taking advantage of a mechanochromic conjugated polydiacetylene (PDA) and the hydrocarbon-induced swelling properties of polydimethylsiloxane (PDMS), a sensor film that enables simple, colorimetric differentiation between a variety of C5 to C14 aliphatic hydrocarbons is fabricated. The unprecedented PDA–PDMS composite sensor undergoes a blue-to-red colorimetric transition on a timescale that is dependent on the chain length of the hydrocarbon target. In addition, the development of the red color is directly proportional to the swelling ratio of the film. This straightforward approach enables naked-eye differentiation between n-pentane and n-heptane. The versatility of the sensor system is demonstrated by using it for the colorimetric determination of kerosene in adulterated diesel oil. Finally, the observation that a PDA microcrystal in the film undergoes significant expansion and tearing in concert with a blue-to-red colorimetric transition during the swelling process provides direct evidence for the mechanism for the mechanochromic behavior of the PDA.