We analyze the end-point region of the photon spectrum in semi-inclusive radiative decays of very heavy quarkonium (m␣ s 2 ӷ⌳ QCD ). We discuss the interplay of the scales arising in the soft-collinear effective theory, m, m(1Ϫz) 1/2 , and m(1Ϫz) for z close to 1, with the scales of heavy quarkonium systems in the weak coupling regime, m, m␣ s , and m␣ s 2 . For 1Ϫzϳ␣ s 2 only collinear and ͑ultra͒soft modes are seen to be relevant, but the recently discovered soft-collinear modes show up for 1ϪzӶ␣ s 2 . The S-and P-wave octet shape functions are calculated. When they are included in the analysis of the photon spectrum of the ⌼(1S) system, the agreement with data in the end-point region becomes excellent. The nonrelativistic QCD matrix elements ͗1 3 S 1 ͉O 8 ( 1 S 0 )͉1 3 S 1 ͘ and ͗1 3 S 1 ͉O 8 ( 3 P J )͉1 3 S 1 ͘ are also obtained.