First off: Make sure you are running the latest version of iPhone software for your phone. Vodacom's settings are automatically present for MMS and tethering in the latest release, and you only have to change it if you are on a different network. If it the default settings do not work even if you are on Vodacom, try these settings as well.

Make sure to read my pointer on MMS at the bottom of this post as well.

Vodacom:

Here is the settings that worked for me:

Important: First set up tethering, then MMS. The tethering config file rewrites the MMS settings, so only do MMS setup after.

First get Internet Tethering settings from here(from your iPhone): http://wan.to/iphone and download the the settings. The phone will tell you it is not official source - ignore that, Vodacom is not helping us.

You will then see that a Internet tethering switch will appear under settings -> General -> Network.

Thereafter, enter the following settings to enable MMS - go to settings - General -> Network -> Cellular Data Network:

Change your Cellular Data settings:


APN: iphone.vodacom.net

MMS settings at the bottom of the screen:
APN: mms.vodacom.net
MMSC: mmsc.vodacom4me.co.za
MMS Proxy: 196.006.128.013:8080

Then got to Settings -> Messages and switch on MMS:



Thereafter, reboot you phone, and go back to cellular data settings to see if the settings "stuck". Then you can start MMS'ing.

MTN:

Important: First set up tethering, then MMS. The tethering config file rewrites the MMS settings, so only do MMS setup after. Here are the settings step for step:

1) Download the MTN Config file here:http://wan.to/iphone, and install it on your phone.


2) Switch on tethering inside settings -> General -> Network -> Internet Tethering. You will notice a blue bar will appear along the top of screen if you are currently "tethered".


Step 3: Reboot your phone, and then enter the following settings at Settings -> General -> Network -> Cellular Data network.

APN: myMTN
Username: mtnmms
Password: mtnmms
MMSC: http://mms.mtn.co.za/mms/wapenc
MMS Proxy: 196.11.240.241:8080


After you have entered these settings, go to Settings -> Messages -> and switch on MMS.

Then reboot your phone, and start enjoying MMS.

(Thank to @ LucasGo for the MTN settings. You can follow him on Twitter)

PS: Just a quick tip on MMS. Currently if you have MMS activated, you will find that combined SMS's (which are more than 160 characters) are automatically sent as a MMS which is not great. If you are on a SMS bundle I would recommend you switch off MMS if you do not want unnecessary charges. MMS is not currently parts of SMS bundles in SA.

PS: Just a quick tip on Internet Tethering: If your iPhone does not show up as another connection on your computer, remember to switch on internet tethering and then reboot the phone. I also recommend you rather use a USB cable than the Bluetooth tethering option. The connection is better, and your battery wont be sucked dry. Enjoy.
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I am a R&D Analyst in Stellenbosch South Africa who has a immense passion for all things tech related. I embrace technology, open source and web standards, and I participate and contribute to the social web.