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Mashing actually does work but good reads and empty jump-ins are also a good way to set up consistent throws. You could also learn some resets. A Strider player threw me three times within 10 seconds using resets.
Official Landmaster of the SSB Wii-U boards! PSN: N00B_SYBORG
The real problem I have with throwing is just finding the right range, and more importantly the right time. For the most part, the key to throwing is just using smart defense, but it is also based on understanding specific weaknesses of individual characters.
Nearly every single character in the roster has at least one move that leaves them wide open for a throw after being guarded. Your first priority should be to learn this. Throws trigger off of one frame, therefore you must find moves that leave the opponent at a -2 disadvantage, or more. Srsly, the game is deliberately designed like this. (*cough* get the guide).
Alot of OTG's will pop someone up off the ground and reset them. If you time it right, you can jump up in the air and throw them (just hold Up+Forward+H). Weskers Samurai low show is probably the most notorious setup, but there are lots of characters that can do it.
Certain characters (not all) also have moves that create very small frame advantages (+1 or +2) upon hit and guard. This allows you to quickly throw after a very brief pause. Chris' low gunshot is perfect for this. Whether it hits or is guarded, you can throw them after a very brief pause.
Finally, i would like to note that the easiest way to score a throw is on someone who is jumping. You can dash up and air throw them with a little practice. Since throws have great priority in this game, use them on players that are jumping around spamming normals (cough wesker). Be careful, though, since certain moves have way more priority and will always beat out a throw.