We used the PW high-repetition laser facility VEGA-3 at Centro de Láseres Pulsados in Salamanca, with the goal of studying the generation of radioisotopes using laser-driven proton beams. Various types of targets have been irradiated, including in particular several targets containing boron to generate α-particles through the hydrogen–boron fusion reaction. We have successfully identified γ-ray lines from several radioisotopes created by irradiation using laser-generated α-particles or protons including ⁴³Sc, ⁴⁴Sc, ⁴⁸Sc, ⁷Be, ¹¹C and ¹⁸F. We show that radioisotope generation can be used as a diagnostic tool to evaluate α-particle generation in laser-driven proton–boron fusion experiments. We also show the production of ¹¹C radioisotopes, $\approx 6 \times 10^{6}$ , and of ⁴⁴Sc radioisotopes, $\approx 5 \times 10^{4}$ per laser shot. This result can open the way to develop laser-driven radiation sources of radioisotopes for medical applications.