The mixed occurrence of s-wave and p-wave contributions in a first forbidden unique Gamow-Teller beta decay has been investigated for the first time by measuring the beta environmental fine structure (BEFS) in a 187Re crystalline compound. The experiment has been carried out with an array of eight AgReO4 thermal detectors operating at a temperature of approximately 100 mK. A fit of the observed BEFS spectrum indicates the p-wave electron emission as the dominant channel. The complete understanding of the BEFS distortion of the 187Re beta decay spectrum is crucial for future experiments aiming at the precise calorimetric measurement of the antineutrino mass.