Phosphine (PH3) has been observed in the atmospheres of Jupiter and Saturn. We have studied the regioselectivity in the gaseous phase of the photochemical addition of PH3 to propene 1, propadiene 2, propyne 3, 1,3-butadiene 4 and 1,3-butadiyne 5. The photolysis were performed at 185 and 254 nm. The volatile products formed in these reactions were characterized by 1H and 31P NMR. The n-propylphosphine 6 and the isopropylphosphine 7 were the major products observed in the photolysis of PH3 with propene. The allylphosphine 8 was obtained when most of the light was absorbed by propene. This allylphosphine was the main product formed in the photolysis of PH3 in the presence of propadiene; the methylvinylphosphine 10 being not detected in these experiments, the reaction presents a very high regioselectivity. When most of the light was absorbed by propadiene, the propargylphosphine 9 was also observed. The photolysis of PH3 in the presence of propyne led to the E- and Z-1-propenylphosphines 12a,b and small amounts of methylvinylphosphine 10. Even when most of the light was absorbed by propyne, the propargylphosphine 9 was not observed. The Z-1-butene-3-ynylphosphine 13a and a mixture of primary phosphines containing the E-and Z-2-butenylphosphines 14a,b were obtained as major products when 1,3-butadiyne and 1,3-butadiene respectively where photolyzed with PH3. A high regioselectivity was thus observed in the photolysis of PH3 with an alkyne or an allene but alkenes led to mixtures of products.