Alginate is utilized to obtain luminescent composite microspheres containing europium tetrakis (dibenzoylmethide) triethylammonium (EuD4TEA) triboluminescent (TL) crystals. Na alginate is initially treated with Ca(II) and then Eu (III) so that physically-crosslinked alginate microspheres were obtained. EuD4TEA crystals are precipitated in situ on the surface of the spheres upon treatment with dibenzoylmethane (DBM) and triethylamine (TEA). The EuD4TEA/alginate composite spheres are swollen in aqueous system, the diameter of the microspheres increases from 180 up to 405 pm in 48 h. TL intensity of the spheres swollen in 1 h decreases 4 folds compared to dry spheres; however, it systematically increases as the swelling time is extended step-wise to 48 h. Swelling may develop structural homogenity in the microsphere that supresses the optical scattering and may lead to better transmittance of the TL signal.