We present the first application of polysiloxane-based scintillators as active medium in a shashlik sampling calorimeter. These results were obtained from a testbeam campaign of a ∼6×6×45 cm3 (13 X0 depth) prototype. A Wavelength Shifting fiber array of 36 elements runs perpendicularly to the stack of iron (15 mm) and polysiloxane scintillator (15 mm) tiles with a density of about one over cm2. Unlike shashlik calorimeters based on plastic organic scintillators, here fibers are optically matched with the scintillator without any intermediate air gap. The prototype features a compact light readout based on Silicon Photo-Multipliers embedded in the bulk of the detector. The detector was tested with electrons, pions and muons with energies ranging from 1 to 7 GeV at the CERN-PS. This solution offers a highly radiation hard detector to instrument the decay region of a neutrino beam, providing an event-by-event measurement of high-angle decay products associated with neutrino production (ENUBET, Enhanced NeUtrino BEams from kaon Tagging, ERC project). The results in terms of light yield, uniformity and energy resolution, are compared to a similar calorimeter built with ordinary plastic scintillators.